The Influence of Targeted Education on Medication Persistence and Generic Substitution among Consumer-Directed Health Care Enrollees

PubMed Central

Sedjo, Rebecca L; Cox, Emily R

2009-01-01

Objective To evaluate an educational outreach among consumer-directed health plan (CDHP) enrollees on medication persistence and lower-cost generic substitution within four chronic medication therapies. Study Setting A cross-sectional analysis using pharmacy claims data from a national employer group that began offering a CDHP in 2006 and implemented an educational outreach to some CDHP enrollees in 2007 was used. Methods The intervention group was comprised of CDHP enrollees who received education outreach and was compared with CDHP enrollees without the educational outreach. Adjusted and unadjusted medication persistence and lower-cost generic substitutions were compared between groups. Principal Findings There was no difference in medication persistence between groups. CDHP enrollees with the educational outreach were more likely to have converted to lower-cost generic alternative antihypertensive medication compared with CDHP enrollees without the educational outreach (ORadj=29.82, 95 percent CI=4.41–201.93). Conclusion Educational outreach directed to CDHP enrollees was associated with increases in lower-cost generic alternatives with no change in patients' chronic medication use. However, considerable opportunity exists to assist CDHP enrollees in making sound health care decisions. PMID:19780849

Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles

DOE PAGES

Kennedy, Zachary C.; Barrett, Christopher A.; Warner, Marvin G.

2017-03-01

Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here in this paper we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediatedmore » decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g –1) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.« less

Sensory Substitution: The Spatial Updating of Auditory Scenes “Mimics” the Spatial Updating of Visual Scenes

PubMed Central

Pasqualotto, Achille; Esenkaya, Tayfun

2016-01-01

Visual-to-auditory sensory substitution is used to convey visual information through audition, and it was initially created to compensate for blindness; it consists of software converting the visual images captured by a video-camera into the equivalent auditory images, or “soundscapes”. Here, it was used by blindfolded sighted participants to learn the spatial position of simple shapes depicted in images arranged on the floor. Very few studies have used sensory substitution to investigate spatial representation, while it has been widely used to investigate object recognition. Additionally, with sensory substitution we could study the performance of participants actively exploring the environment through audition, rather than passively localizing sound sources. Blindfolded participants egocentrically learnt the position of six images by using sensory substitution and then a judgment of relative direction task (JRD) was used to determine how this scene was represented. This task consists of imagining being in a given location, oriented in a given direction, and pointing towards the required image. Before performing the JRD task, participants explored a map that provided allocentric information about the scene. Although spatial exploration was egocentric, surprisingly we found that performance in the JRD task was better for allocentric perspectives. This suggests that the egocentric representation of the scene was updated. This result is in line with previous studies using visual and somatosensory scenes, thus supporting the notion that different sensory modalities produce equivalent spatial representation(s). Moreover, our results have practical implications to improve training methods with sensory substitution devices (SSD). PMID:27148000

Enhanced osteoconductivity of sodium-substituted hydroxyapatite by system instability.

PubMed

Sang Cho, Jung; Um, Seung-Hoon; Su Yoo, Dong; Chung, Yong-Chae; Hye Chung, Shin; Lee, Jeong-Cheol; Rhee, Sang-Hoon

2014-07-01

The effect of substituting sodium for calcium on enhanced osteoconductivity of hydroxyapatite was newly investigated. Sodium-substituted hydroxyapatite was synthesized by reacting calcium hydroxide and phosphoric acid with sodium nitrate followed by sintering. As a control, pure hydroxyapatite was prepared under identical conditions, but without the addition of sodium nitrate. Substitution of calcium with sodium in hydroxyapatite produced the structural vacancies for carbonate ion from phosphate site and hydrogen ion from hydroxide site of hydroxyapatite after sintering. The total system energy of sodium-substituted hydroxyapatite with structural defects calculated by ab initio methods based on quantum mechanics was much higher than that of hydroxyapatite, suggesting that the sodium-substituted hydroxyapatite was energetically less stable compared with hydroxyapatite. Indeed, sodium-substituted hydroxyapatite exhibited higher dissolution behavior of constituent elements of hydroxyapatite in simulated body fluid (SBF) and Tris-buffered deionized water compared with hydroxyapatite, which directly affected low-crystalline hydroxyl-carbonate apatite forming capacity by increasing the degree of apatite supersaturation in SBF. Actually, sodium-substituted hydroxyapatite exhibited markedly improved low-crystalline hydroxyl-carbonate apatite forming capacity in SBF and noticeably higher osteoconductivity 4 weeks after implantation in calvarial defects of New Zealand white rabbits compared with hydroxyapatite. In addition, there were no statistically significant differences between hydroxyapatite and sodium-substituted hydroxyapatite on cytotoxicity as determined by BCA assay. Taken together, these results indicate that sodium-substituted hydroxyapatite with structural defects has promising potential for use as a bone grafting material due to its enhanced osteoconductivity compared with hydroxyapatite. © 2013 Wiley Periodicals, Inc.

In vivo gene correction with targeted sequence substitution through microhomology-mediated end joining.

PubMed

Shin, Jeong Hong; Jung, Soobin; Ramakrishna, Suresh; Kim, Hyongbum Henry; Lee, Junwon

2018-07-07

Genome editing technology using programmable nucleases has rapidly evolved in recent years. The primary mechanism to achieve precise integration of a transgene is mainly based on homology-directed repair (HDR). However, an HDR-based genome-editing approach is less efficient than non-homologous end-joining (NHEJ). Recently, a microhomology-mediated end-joining (MMEJ)-based transgene integration approach was developed, showing feasibility both in vitro and in vivo. We expanded this method to achieve targeted sequence substitution (TSS) of mutated sequences with normal sequences using double-guide RNAs (gRNAs), and a donor template flanking the microhomologies and target sequence of the gRNAs in vitro and in vivo. Our method could realize more efficient sequence substitution than the HDR-based method in vitro using a reporter cell line, and led to the survival of a hereditary tyrosinemia mouse model in vivo. The proposed MMEJ-based TSS approach could provide a novel therapeutic strategy, in addition to HDR, to achieve gene correction from a mutated sequence to a normal sequence. Copyright © 2018 Elsevier Inc. All rights reserved.

Selective Attention with Human Earphones.

ERIC Educational Resources Information Center

Goodwin, C. James

1988-01-01

Describes a method for demonstrating dichotic listening tasks in the classroom which involves substituting live readers for tape recorded messages to allow direct student observation of various selective attention phenomena. Concludes that live readers offer pedagogical benefits that make them superior to tape recorded dichotic listening tasks.…

Some new results on stability and synchronization for delayed inertial neural networks based on non-reduced order method.

PubMed

Li, Xuanying; Li, Xiaotong; Hu, Cheng

2017-12-01

In this paper, without transforming the second order inertial neural networks into the first order differential systems by some variable substitutions, asymptotic stability and synchronization for a class of delayed inertial neural networks are investigated. Firstly, a new Lyapunov functional is constructed to directly propose the asymptotic stability of the inertial neural networks, and some new stability criteria are derived by means of Barbalat Lemma. Additionally, by designing a new feedback control strategy, the asymptotic synchronization of the addressed inertial networks is studied and some effective conditions are obtained. To reduce the control cost, an adaptive control scheme is designed to realize the asymptotic synchronization. It is noted that the dynamical behaviors of inertial neural networks are directly analyzed in this paper by constructing some new Lyapunov functionals, this is totally different from the traditional reduced-order variable substitution method. Finally, some numerical simulations are given to demonstrate the effectiveness of the derived theoretical results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of adequate pelvic floor muscle contraction on the movement of the coccyx during pelvic floor muscle training.

PubMed

Fujisaki, Akiko; Shigeta, Miwa; Shimoinaba, Misa; Yoshimura, Yasukuni

2018-04-01

[Purpose] Pelvic floor muscle training is a first-line therapy for female stress urinary incontinence. Previous studies have suggested that the coccyx tip moves ventrally and cranially during pelvic floor muscle contraction. The study aimed to elucidate the influence of adequate pelvic floor muscle contraction on coccyx movement. [Subjects and Methods] Sixty-three females (57 patients with stress urinary incontinence and additional 6 healthy volunteers) were enrolled. Using magnetic resonance imaging, coccyx movement was evaluated during pelvic floor muscle contraction and strain. An adequate contraction was defined as a contraction with good Oxford grading scale [≥3] and without inadequate muscle substitution patterns. [Results] Inadequate muscle substitution patterns were observed in 33 participants (52.4%). No significant difference was observed in the movement of the coccyx tip in the ventrodorsal direction between females with and without inadequate muscle substitution patterns. However, a significant increase in the movement of the coccyx tip in the cranial direction was detected in the group without inadequate muscle substitution patterns. Compared to participants with inadequate pelvic floor muscle contraction, those who had adequate pelvic floor muscle contraction exhibited significantly increased cranial movement of the coccyx. [Conclusion] Adequate pelvic floor muscle contraction can produce cranial movement of the coccyx tip.

Assessment of the mutagenic potential of ethanol auto engine exhaust gases by the Salmonella typhimurium microsomal mutagenesis assay, using a direct exposure method.

PubMed

Lotfi, C F; Brentani, M M; Böhm, G M

1990-08-01

The mutagenic activity of the new Brazilian fuel, ethanol, was determined by employing the Salmonella typhimurium microsomal mutagenesis assay (TA97, TA98, TA100, TA102, and TA104) and a direct exposure method. This methodology was first used to determine the mutagenic activity of gasoline, revealing mutagenic activity of base-pair substitution without any need for metabolic activation, indicating the presence of direct-action mutagens. Experiments with ethanol suggest an indirect mutagenic activity of the oxidant type. The exposure system was considered suitable for future studies of gaseous mixtures.

Multiple heteroatom substitution to graphene nanoribbon

PubMed Central

Meyer, Ernst

2018-01-01

Substituting heteroatoms into nanostructured graphene elements, such as graphene nanoribbons, offers the possibility for atomic engineering of electronic properties. To characterize these substitutions, functionalized atomic force microscopy (AFM)—a tool to directly resolve chemical structures—is one of the most promising tools, yet the chemical analysis of heteroatoms has been rarely performed. We synthesized multiple heteroatom-substituted graphene nanoribbons and showed that AFM can directly resolve elemental differences and can be correlated to the van der Waals radii, as well as the modulated local electron density caused by the substitution. This elemental-sensitive measurement takes an important step in the analysis of functionalized two-dimensional carbon materials. PMID:29662955

19 CFR 191.2 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-04-01

... under the provision for the substitution of finished petroleum derivatives, § 313(p), as amended (19 U.S... identified for purposes of direct identification drawback by use of the accounting methods provided for in... (CONTINUED) DRAWBACK General Provisions § 191.2 Definitions. For the purposes of this part: (a) Abstract...

Extending substructure based iterative solvers to multiple load and repeated analyses

NASA Technical Reports Server (NTRS)

Farhat, Charbel

1993-01-01

Direct solvers currently dominate commercial finite element structural software, but do not scale well in the fine granularity regime targeted by emerging parallel processors. Substructure based iterative solvers--often called also domain decomposition algorithms--lend themselves better to parallel processing, but must overcome several obstacles before earning their place in general purpose structural analysis programs. One such obstacle is the solution of systems with many or repeated right hand sides. Such systems arise, for example, in multiple load static analyses and in implicit linear dynamics computations. Direct solvers are well-suited for these problems because after the system matrix has been factored, the multiple or repeated solutions can be obtained through relatively inexpensive forward and backward substitutions. On the other hand, iterative solvers in general are ill-suited for these problems because they often must restart from scratch for every different right hand side. In this paper, we present a methodology for extending the range of applications of domain decomposition methods to problems with multiple or repeated right hand sides. Basically, we formulate the overall problem as a series of minimization problems over K-orthogonal and supplementary subspaces, and tailor the preconditioned conjugate gradient algorithm to solve them efficiently. The resulting solution method is scalable, whereas direct factorization schemes and forward and backward substitution algorithms are not. We illustrate the proposed methodology with the solution of static and dynamic structural problems, and highlight its potential to outperform forward and backward substitutions on parallel computers. As an example, we show that for a linear structural dynamics problem with 11640 degrees of freedom, every time-step beyond time-step 15 is solved in a single iteration and consumes 1.0 second on a 32 processor iPSC-860 system; for the same problem and the same parallel processor, a pair of forward/backward substitutions at each step consumes 15.0 seconds.

Enantioselective Synthesis of 2-Amino-1,1-diarylalkanes Bearing a Carbocyclic Ring Substituted Indole through Asymmetric Catalytic Reaction of Hydroxyindoles with Nitroalkenes.

PubMed

Vila, Carlos; Rostoll-Berenguer, Jaume; Sánchez-García, Rubén; Blay, Gonzalo; Fernández, Isabel; Muñoz, M Carmen; Pedro, José R

2018-06-07

An asymmetric catalytic reaction of hydroxyindoles with nitroalkenes leading to the Friedel-Crafts alkylation in the carbocyclic ring of indole is presented. The method is based on the activating/directing effects of the hydroxy group situated in the carbocyclic ring of the indole providing nitroalkylated indoles functionalizated at the C-4, C-5, and C-7 positions with high yield, regio-, and enantioselectivity. The optically enriched nitroalkanes were transformed efficiently in optically enriched 2-amino-1,1-diarylalkanes bearing a carbocyclic ring substituted indole.

Diastereoselective Pyrrolidine Synthesis via Copper Promoted Intramolecular Aminooxygenation of Alkenes; Formal Synthesis of (+)-Monomorine

PubMed Central

Paderes, Monissa C; Chemler, Sherry R

2009-01-01

The diastereoselectivity of the copper-promoted intramolecular aminooxygenation of various alkene substrates was investigated. α-Substituted 4-pentenyl sulfonamides favor the formation of 2,5-cis-pyrrolidines (dr >20:1) giving excellent yields which range from 76–97% while γ-substituted substrates favor the 2,3-trans pyrrolidine adducts with moderate selectivity (ca. 3:1). A substrate whose N-substituent was directly tethered to the α-carbon exclusively yielded the 2,5-trans pyrrolidine. The synthetic utility of the method was demonstrated by a short and efficient formal synthesis of (+)-monomorine. PMID:19331361

Calibration of High Frequency MEMS Microphones

NASA Technical Reports Server (NTRS)

Shams, Qamar A.; Humphreys, William M.; Bartram, Scott M.; Zuckewar, Allan J.

2007-01-01

Understanding and controlling aircraft noise is one of the major research topics of the NASA Fundamental Aeronautics Program. One of the measurement technologies used to acquire noise data is the microphone directional array (DA). Traditional direction array hardware, consisting of commercially available condenser microphones and preamplifiers can be too expensive and their installation in hard-walled wind tunnel test sections too complicated. An emerging micro-machining technology coupled with the latest cutting edge technologies for smaller and faster systems have opened the way for development of MEMS microphones. The MEMS microphone devices are available in the market but suffer from certain important shortcomings. Based on early experiments with array prototypes, it has been found that both the bandwidth and the sound pressure level dynamic range of the microphones should be increased significantly to improve the performance and flexibility of the overall array. Thus, in collaboration with an outside MEMS design vendor, NASA Langley modified commercially available MEMS microphone as shown in Figure 1 to meet the new requirements. Coupled with the design of the enhanced MEMS microphones was the development of a new calibration method for simultaneously obtaining the sensitivity and phase response of the devices over their entire broadband frequency range. Over the years, several methods have been used for microphone calibration. Some of the common methods of microphone calibration are Coupler (Reciprocity, Substitution, and Simultaneous), Pistonphone, Electrostatic actuator, and Free-field calibration (Reciprocity, Substitution, and Simultaneous). Traditionally, electrostatic actuators (EA) have been used to characterize air-condenser microphones for wideband frequency ranges; however, MEMS microphones are not adaptable to the EA method due to their construction and very small diaphragm size. Hence a substitution-based, free-field method was developed to calibrate these microphones at frequencies up to 80 kHz. The technique relied on the use of a random, ultrasonic broadband centrifugal sound source located in a small anechoic chamber. Phase calibrations of the MEMS microphones were derived from cross spectral phase comparisons between the reference and test substitution microphones and an adjacent and invariant grazing-incidence 1/8-inch standard microphone.

Charge Transfer Directed Radical Substitution Enables para-Selective C–H Functionalization

PubMed Central

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

2016-01-01

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 which enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit areneto-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate that the selectivity is predictable by a simple theoretical tool 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 charge transfer directed radical substitution could serve as the basis for the development of new, highly selective C–H functionalization reactions. PMID:27442288

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.

Efficient synthesis of anacardic acid analogues and their antibacterial activities.

PubMed

Mamidyala, Sreeman K; Ramu, Soumya; Huang, Johnny X; Robertson, Avril A B; Cooper, Matthew A

2013-03-15

Anacardic acid derivatives exhibit a broad range of biological activities. In this report, an efficient method for the synthesis of anacardic acid derivatives was explored, and a small set of salicylic acid variants synthesised retaining a constant hydrophobic element (a naphthyl tail). The naphthyl side chain was introduced via Wittig reaction and the aldehyde installed using directed ortho-metalation reaction of the substituted o-anisic acids. The failure of ortho-metalation using unprotected carboxylic acid group compelled us to use directed ortho-metalation in which a tertiary amide was used as a strong ortho-directing group. In the initial route, tertiary amide cleavage during final step was challenging, but cleaving the tertiary amide before Wittig reaction was beneficial. The Wittig reaction with protected carboxylic group (methyl ester) resulted in side-products whereas using sodium salt resulted in higher yields. The novel compounds were screened for antibacterial activity and cytotoxicity. Although substitution on the salicylic head group enhanced antibacterial activities they also enhanced cytotoxicity. Copyright © 2013 Elsevier Ltd. All rights reserved.

40 CFR Appendix G to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes Listed in the March 3, 1999...

Code of Federal Regulations, 2010 CFR

2010-07-01

.... Refrigerants Unacceptable Substitutes End-use Substitute Decision Comments CFC-12, R-502, and HCFC-22 Household... gas emissions from direct release of refrigerant to the atmosphere. [64 FR 10378, Mar. 3, 1999] ...

40 CFR Appendix G to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes Listed in the March 3, 1999...

Code of Federal Regulations, 2011 CFR

2011-07-01

.... Refrigerants Unacceptable Substitutes End-use Substitute Decision Comments CFC-12, R-502, and HCFC-22 Household... gas emissions from direct release of refrigerant to the atmosphere. [64 FR 10378, Mar. 3, 1999] ...

Preparation of mesoporous Cs-POM@MOF-199@MCM-41 under two different synthetic methods for a highly oxidesulfurization of dibenzothiophene.

PubMed

Li, Si-Wen; Li, Jia-Rong; Jin, Qi-Ping; Yang, Zhi; Zhang, Rong-Lan; Gao, Rui-Min; Zhao, Jian-She

2017-09-05

Two different synthetic methods, the direct method and the substitution method, were used to synthesize the Cs-POM@MOF-199@MCM-41 (Cs-PMM), in which the modified heteropolyacid with cesium salt has been encapsulated into the pores with the mixture of MOF and MCM-41. The structural properties of the as-prepared catalysts were characterized using various analytical techniques: powder X-ray diffraction, FT-IR, SEM, TEM, XPS and BET, confirming that the Cs-POM active species retained its Keggin structure after immobilization. The substitution method of Cs-PMM exhibited more excellent catalytic performance for oxidative desulfurization of dibenzothiophene in the presence of oxygen. Under optimal conditions, the DBT conversion rate reached up to 99.6% and could be recycled 10 times without significant loss of catalytic activity, which is mainly attributed to the slow leaching of the active heteropolyacid species from the strong fixed effect of the mixture porous materials. Copyright © 2017. Published by Elsevier B.V.

Equivalent-Continuum Modeling of Nano-Structured Materials

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Gates, Thomas S.; Nicholson, Lee M.; Wise, Kristopher E.

2001-01-01

A method has been developed for modeling structure-property relationships of nano-structured materials. This method serves as a link between computational chemistry and solid mechanics by substituting discrete molecular structures with an equivalent-continuum model. It has been shown that this substitution may be accomplished by equating the vibrational potential energy of a nano-structured material with the strain energy of representative truss and continuum models. As an important example with direct application to the development and characterization of single-walled carbon nanotubes, the model has been applied to determine the effective continuum geometry of a graphene sheet. A representative volume element of the equivalent-continuum model has been developed with an effective thickness. This effective thickness has been shown to be similar to, but slightly smaller than, the interatomic spacing of graphite.

A GC-MS method for the detection of toluene and ethylbenzene in volatile substance abuse.

PubMed

El-Haj, B M; Al-Amri, A M; Hassan, M H; Bin-Khadem, R K; Al-Hadi, A A

2000-09-01

The interference of some substances with the gas chromatography-flame ionization detection and gas chromatography-Fourier transform infrared detection of toluene and ethylbenzene in volatile substance abuse poses problems. A gas chromatography-mass spectrometry (GC-MS) method that will overcome such interference has been developed for the detection of toluene and/or ethylbenzene in the headspace of preparations and products containing these substances and in the headspace of blood samples in the cases of volatile substance abuse. The method is based on converting toluene to benzoic acid via the formation of benzotrichloride. The latter compound was obtained upon the reaction of toluene with chlorine gas under direct sunlight conditions. In the presence of water, benzotrichloride was converted to benzoic acid. Ethylbenzene was converted to benzoic acid and two phenylethanols via the formation of side chain chloro-substituted phenylethanes followed by reaction with water. The chloro-substituted phenylethanes were obtained by the reaction of ethylbenzene with chlorine under direct sunlight conditions. The benzoic acid resulting from toluene and/or ethylbenzene and the two phenylethanols resulting from ethylbenzene were detected by GC-MS as their trimethylsilyl (TMS) derivatives. For the method to be viable for the detection of volatile substance abuse, the chlorination reactions were effected in the gaseous state.

Determination of fluoride in oxides with the fluoride-ion activity electrode.

PubMed

Peters, M A; Ladd, D M

1971-07-01

The application of the fluoride-ion activity electrode to the determination of fluoride in various samples has been studied. Samples are decomposed by fusion and the fluoride concentration is determined by a standard-addition or a direct method. The standard-addition method is unsuitable, owing to a positive bias. The direct method, however, is rapid, accurate and precise. The fluoride content of exploration ores, fluorspar, opal glass, phosphate rock and various production samples, has been successfully determined. The success of the direct method depends on the effectiveness of the system used to buffer pH and ionic strength and complex possible interferences (Al(3+), Ca(2+), Fe(3+)). The effect of interferences has been studied and found to be minimal. The procedures are rapid and accurate and may be substituted for the traditional Willard and Winter or pyro hydrolysis methods, with considerable saving of time.

21 CFR 184.1259 - Cocoa butter substitute.

Code of Federal Regulations, 2013 CFR

2013-04-01

..._locations.html. (9) Hexane—not more than 5 parts per million as determined by the method of Dupuy et al., “Rapid Quantitative Determination of Residual Hexane in Oils by Direct Gas Chromatography,” published in... good manufacturing practice: Confections and frostings as defined in § 170.3(n)(9) of this chapter...

21 CFR 184.1259 - Cocoa butter substitute.

Code of Federal Regulations, 2012 CFR

2012-04-01

..._locations.html. (9) Hexane—not more than 5 parts per million as determined by the method of Dupuy et al., “Rapid Quantitative Determination of Residual Hexane in Oils by Direct Gas Chromatography,” published in... good manufacturing practice: Confections and frostings as defined in § 170.3(n)(9) of this chapter...

Quantifying reactivity for electrophilic aromatic substitution reactions with Hirshfeld charge.

PubMed

Liu, Shubin

2015-03-26

An electrophilic aromatic substitution is a process where one atom or group on an aromatic ring is replaced by an incoming electrophile. The reactivity and regioselectivity of this category of reactions is significantly impacted by the group that is already attached to the aromatic ring. Groups promoting substitution at the ortho/para and meta position are called ortho/para and meta directing groups, respectively. Earlier, we have shown that regioselectivity of the electrophilic aromatic substitution is dictated by the nucleophilicity of the substituted aromatic ring, which is proportional to the Hirshfeld charge on the regioselective site. Ortho/para directing groups have the largest negative charge values at the ortho/para positions, whereas meta directing groups often have the largest negative charge value at the meta position. The electron donation or acceptance feature of a substitution group is irrelevant to the regioselectivity. In this contribution, we extend our previous study by quantifying the reactivity for this kind of reactions. To that end, we examine the transition-state structure and activation energy of an identity reaction for a series of monosubstituted-benzene molecules reacting with hydrogen fluoride using BF3 as the catalyst in the gas phase. A total of 18 substitution groups will be considered, nine of which are ortho/para directing and the other nine groups meta directing. From this study, we found that the barrier height of these reactions strongly correlates with the Hirshfeld charge on the regioselective site for both ortho/para and meta directing groups, with the correlation coefficient R(2) both better than 0.96. We also discovered a less accurate correlation between the barrier height and HOMO energy. These results reconfirm the validity and effectiveness of employing the Hirshfeld charge as a reliable descriptor of both reactivity and regioselectivity for this vastly important category of chemical transformations.

Determining orientation and direction of DNA sequences

DOEpatents

Goodwin, Edwin H.; Meyne, Julianne

2000-01-01

Determining orientation and direction of DNA sequences. A method by which fluorescence in situ hybridization can be made strand specific is described. Cell cultures are grown in a medium containing a halogenated nucleotide. The analog is partially incorporated in one DNA strand of each chromatid. This substitution takes place in opposite strands of the two sister chromatids. After staining with the fluorescent DNA-binding dye Hoechst 33258, cells are exposed to long-wavelength ultraviolet light which results in numerous strand nicks. These nicks enable the substituted strand to be denatured and solubilized by heat, treatment with high or low pH aqueous solutions, or by immersing the strands in 2.times.SSC (0.3M NaCl+0.03M sodium citrate), to name three procedures. It is unnecessary to enzymatically digest the strands using Exo III or another exonuclease in order to excise and solubilize nucleotides starting at the sites of the nicks. The denaturing/solubilizing process removes most of the substituted strand while leaving the prereplication strand largely intact. Hybridization of a single-stranded probe of a tandem repeat arranged in a head-to-tail orientation will result in hybridization only to the chromatid with the complementary strand present.

Mono- and Di-Alkylation Processes of DNA Bases by Nitrogen Mustard Mechlorethamine.

PubMed

Larrañaga, Olatz; de Cózar, Abel; Cossío, Fernando P

2017-12-06

The reactivity of nitrogen mustard mechlorethamine (mec) with purine bases towards formation of mono- (G-mec and A-mec) and dialkylated (AA-mec, GG-mec and AG-mec) adducts has been studied using density functional theory (DFT). To gain a complete overview of DNA-alkylation processes, direct chloride substitution and formation through activated aziridinium species were considered as possible reaction paths for adduct formation. Our results confirm that DNA alkylation by mec occurs via aziridine intermediates instead of direct substitution. Consideration of explicit water molecules in conjunction with polarizable continuum model (PCM) was shown as an adequate computational method for a proper representation of the system. Moreover, Runge-Kutta numerical kinetic simulations including the possible bisadducts have been performed. These simulations predicted a product ratio of 83:17 of GG-mec and AG-mec diadducts, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The antigenic surface of staphylococcal nuclease. II. Analysis of the N-1 epitope by site-directed mutagenesis.

PubMed

Smith, A M; Benjamin, D C

1991-02-15

Previous studies in our laboratory on the production and isolation of a panel of mAb to staphylococcal nuclease allowed us to define a series of eight overlapping epitopes. Using site-directed mutagenesis of the nuclease coding sequences we were able to map the nonoverlapping epitopes recognized by two members of this panel. In the study reported here, we report the generation and analysis of a number of single amino acid substitutions for seven surface residues predicted to lie within one of these two epitopes. Immunochemical analysis showed that one or more substitutions at each of these seven positions had a major effect on mAb binding, whereas other substitutions had none. Based on the nature of these substitutions and the chemical and physical properties of the variant molecules, we believe that any structural effects induced by these substitutions are local and do not result in long-range structural alterations that indirectly influence antibody reactivity. Therefore, we conclude that disruption of mAb binding can be directly attributed to changes in amino acid side chains and that not only are all seven of the residues studied part of the epitope but all seven make contact with the antibody combining site. These studies demonstrate the advantages of using site-directed mutagenesis to study antigen structure and emphasize the importance of constructing the examining multiple substitutions for any given amino acid.

Growth of epitaxial orthorhombic YO{sub 1.5}-substituted HfO{sub 2} thin film

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

Shimizu, Takao; Katayama, Kiliha; Kiguchi, Takanori

YO{sub 1.5}-substituted HfO{sub 2} thin films with various substitution amounts were grown on (100) YSZ substrates by the pulsed laser deposition method directly from the vapor phase. The epitaxial growth of film with different YO{sub 1.5} amounts was confirmed by the X-ray diffraction method. Wide-area reciprocal lattice mapping measurements were performed to clarify the crystal symmetry of films. The formed phases changed from low-symmetry monoclinic baddeleyite to high-symmetry tetragonal/cubic fluorite phases through an orthorhombic phase as the YO{sub 1.5} amount increased from 0 to 0.15. The additional annular bright-field scanning transmission electron microscopy indicates that the orthorhombic phase has polarmore » structure. This means that the direct growth by vapor is of polar orthorhombic HfO{sub 2}-based film. Moreover, high-temperature X-ray diffraction measurements showed that the film with a YO{sub 1.5} amount of 0.07 with orthorhombic structure at room temperature only exhibited a structural phase transition to tetragonal phase above 450 °C. This temperature is much higher than the reported maximum temperature of 200 °C to obtain ferroelectricity as well as the expected temperature for real device application. The growth of epitaxial orthorhombic HfO{sub 2}-based film helps clarify the nature of ferroelectricity in HfO{sub 2}-based films (186 words/200 words)« less

12 CFR 567.1 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-01-01

... extension or renewal and upon a new, bona fide credit analysis utilizing current information on financial... means a financial institution that engages in the business of banking; that is recognized as a bank by... assumption of any credit risk is a direct credit substitute. Direct credit substitutes include: (1) Financial...

12 CFR 567.1 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... extension or renewal and upon a new, bona fide credit analysis utilizing current information on financial... means a financial institution that engages in the business of banking; that is recognized as a bank by... assumption of any credit risk is a direct credit substitute. Direct credit substitutes include: (1) Financial...

12 CFR 567.1 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

... extension or renewal and upon a new, bona fide credit analysis utilizing current information on financial... means a financial institution that engages in the business of banking; that is recognized as a bank by... assumption of any credit risk is a direct credit substitute. Direct credit substitutes include: (1) Financial...

12 CFR 567.1 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

... extension or renewal and upon a new, bona fide credit analysis utilizing current information on financial... means a financial institution that engages in the business of banking; that is recognized as a bank by... assumption of any credit risk is a direct credit substitute. Direct credit substitutes include: (1) Financial...

Maximum parsimony, substitution model, and probability phylogenetic trees.

PubMed

Weng, J F; Thomas, D A; Mareels, I

2011-01-01

The problem of inferring phylogenies (phylogenetic trees) is one of the main problems in computational biology. There are three main methods for inferring phylogenies-Maximum Parsimony (MP), Distance Matrix (DM) and Maximum Likelihood (ML), of which the MP method is the most well-studied and popular method. In the MP method the optimization criterion is the number of substitutions of the nucleotides computed by the differences in the investigated nucleotide sequences. However, the MP method is often criticized as it only counts the substitutions observable at the current time and all the unobservable substitutions that really occur in the evolutionary history are omitted. In order to take into account the unobservable substitutions, some substitution models have been established and they are now widely used in the DM and ML methods but these substitution models cannot be used within the classical MP method. Recently the authors proposed a probability representation model for phylogenetic trees and the reconstructed trees in this model are called probability phylogenetic trees. One of the advantages of the probability representation model is that it can include a substitution model to infer phylogenetic trees based on the MP principle. In this paper we explain how to use a substitution model in the reconstruction of probability phylogenetic trees and show the advantage of this approach with examples.

Precise through-space control of an abiotic electrophilic aromatic substitution reaction

NASA Astrophysics Data System (ADS)

Murphy, Kyle E.; Bocanegra, Jessica L.; Liu, Xiaoxi; Chau, H.-Y. Katharine; Lee, Patrick C.; Li, Jianing; Schneebeli, Severin T.

2017-04-01

Nature has evolved selective enzymes for the efficient biosynthesis of complex products. This exceptional ability stems from adapted enzymatic pockets, which geometrically constrain reactants and stabilize specific reactive intermediates by placing electron-donating/accepting residues nearby. Here we perform an abiotic electrophilic aromatic substitution reaction, which is directed precisely through space. Ester arms--positioned above the planes of aromatic rings--enable it to distinguish between nearly identical, neighbouring reactive positions. Quantum mechanical calculations show that, in two competing reaction pathways, both [C-H...O]-hydrogen bonding and electrophile preorganization by coordination to a carbonyl group likely play a role in controlling the reaction. These through-space-directed mechanisms are inspired by dimethylallyl tryptophan synthases, which direct biological electrophilic aromatic substitutions by preorganizing dimethylallyl cations and by stabilizing reactive intermediates with [C-H...N]-hydrogen bonding. Our results demonstrate how the third dimension above and underneath aromatic rings can be exploited to precisely control electrophilic aromatic substitutions.

Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-Ray Structures, Optical and Electronic Properties

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

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue-Bin

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay- and ortho-substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Moreover, analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects from substituting electron-withdrawing groups at all three positions.« less

Core Perylene Diimide Designs via Direct Bay and Ortho (Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties

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

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue B.

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay and ortho substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects of electron withdrawing group substitution at all three positions.« less

Asymmetry in Object Substitution Masking Occurs Relative to the Direction of Spatial Attention Shift

ERIC Educational Resources Information Center

Hirose, Nobuyuki; Osaka, Naoyuki

2010-01-01

A sparse mask that persists beyond the duration of a target can reduce its visibility, a phenomenon called "object substitution masking". Y. Jiang and M. M. Chun (2001a) found an asymmetric pattern of substitution masking such that a mask on the peripheral side of the target caused stronger substitution masking than on the central side.…

Different effects of the two types of spatial pre-cueing: what precisely is "attention" in Di Lollo's and Enns' substitution masking theory?

PubMed

Luiga, I; Bachmann, T

2007-11-01

Enns and Di Lollo [Psychological Science, 8 (2), 135-139, 1997] have introduced the object substitution theory of visual masking. Object substitution masking occurs when focusing attention on the target is delayed. However, Posner (Quarterly Journal of Experimental Psychology, 32, 3-25, 1980) has already shown that attention can be directed to a target at least in two ways: intentionally (endogenously) and automatically (exogenously). We conducted two experiments to explore the effects of endogenous and exogenous cues on substitution masking. The results showed that when attention was shifted to the target location automatically (using a local peripheral pre-cue), masking was attenuated. A decrease in target identification dependent on a delay of mask offset, typical to substitution masking, was not observed. However, strong substitution masking occurred when the target location was not pre-cued or when attention was directed to the target location intentionally (using a symbolic pre-cue displayed centrally). The hypothesis of two different mechanisms of attentional control in substitution masking was confirmed.

A novel method of carbon dioxide clumped isotope analysis with tunable infra-red laser direct absorption spectroscopy

NASA Astrophysics Data System (ADS)

Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

2016-04-01

Precise clumped isotopes analysis of carbon dioxide opens up new horizons of atmospheric and biogeochemical research. Recent advances in laser and spectroscopic techniques provides us necessary instrumentation to access extremely low sub-permill variations of multiply-substituted isotopologues. We present an advanced analysis method of carbon dioxide clumped isotopes using direct absorption spectroscopy. Our assessments predict the ultimate precision of the new method on the sub-permill level comparable to state of the art mass spectrometry. Among the most auspicious intrinsic properties of this method we highlight genuine Δ16O13C18O and Δ16O13C18O measurements without isobaric interference, measurement cycle duration of several minutes versus hours for mass spectrometric analysis, reduced sample size of ˜ 10 μmol and high flexibility, allowing us to perform in-situ measurements. The pilot version of the instrument is being developed in an international collaboration framework between Heidelberg University, Germany and Pierre and Marie Curie University, Paris, France. It employs two continuous interband quantum cascade lasers tuned at 4.439 μm and 4.329 μm to measure doubly ( 16O13C18O, 16O13C17O) and singly ( 16O12C16O, 16O13C16O, 16O12C17O, 16O12C18O) substituted isotopologues, respectively. Two identical Herriot cells are filled with dry pure CO2 sample and reference gas at working pressure of 1 - 10 mbar. Cells provide optical path lengths of ˜ 17 m for the laser tuned at doubly substituted isotopologues lines and use a single pass for the laser tuned at the stronger lines of singly substituted isotopologues. Light outside of the gas cells is coupled into optical fiber to avoid absorption by ambient air CO2. Simulations predict sub-permill precision at working pressure of 1 mbar and room temperature stabilised at the ±10 mK level. Our prime target is to apply the proposed method for continuous in-situ analysis of CO2. We are foreseeing potential applications to the following environmental issues: assessments of distinct sources of atmospheric CO2, temperature reconstructions from terrestrial and marine archives, extra-terrestrial atmosphere studies, etc.

Directly oxidized chemiluminescence of 2-substituted-4,5-di(2-furyl)-1H -imidazole by acidic potassium permanganate and its analytical application for determination of albumin.

PubMed

Kang, Jing; Zhang, Yumin; Huang, Zhongxiu; Han, Lu; Tang, Jieli; Wang, Shuaijun; Zhang, Yihua

2011-07-01

In the paper, 2,4,5-tri(2-furyl)-1H-imidazole (TFI) and 2-phenyl-4,5-di(2-furyl)-1H-imidazole (PDFI), were chosen to investigate chemiluminescence (CL) properties of 2-substituted-4,5-di(2-furyl)-1H-imidazoles. The directly oxidized CL of analytes by potassium permanganate (KMnO(4)) was in detail studied. The KMnO(4) could directly oxidize TFI/PDFI to produce strong CL emission in acidic solution. The effects of experimental conditions were investigated. Under the optimal conditions, the effect of albumin on the TFI/PDFI-KMnO(4) system was investigated. It was found that the addition of albumin into the system could induce enhancement of CL signal, and the enhanced CL intensity is linearly related to the logarithm of concentration of albumin. Based on this study, a novel CL method has been developed for the determination of albumin with high sensitivity and good selectivity. The method was applied to the determination of albumin in human serum samples, and the results were in agreement with those obtained by the bromcresol green (BCG) method. The relative errors for the analytical results were from -5.8% to 4.2%. These new phenomena would further enable people to exploit more CL analytical application of the heterocyclic imidazole derivatives. © Springer Science+Business Media, LLC 2011

Intrinsically modified thermoelectric performance of alkaline-earth isovalently substituted [Bi2AE2O4][CoO2]y single crystals

NASA Astrophysics Data System (ADS)

Sun, N.; Dong, S. T.; Zhang, B. B.; Chen, Y. B.; Zhou, J.; Zhang, S. T.; Gu, Z. B.; Yao, S. H.; Chen, Y. F.

2013-07-01

Alkaline-earth elements isovalently substituted into a [Bi2AE2O4][CoO2]y (AE2 = Ca2, Sr2, and CaSr) single crystal with a layered structure were grown by the optical floating zone method. Structural characterization by X-ray diffraction and electron microscopy showed that the layers were oriented perpendicular to the c-axis, as well as the growth of direction was parallel to the ab-plane. The thermoelectric properties, including the Seebeck effect, electrical conductivity and thermal conductivity were investigated. The results of the thermoelectric measurements showed that the full substitution of Ca for Sr in [Bi2Sr2-xCaxO4][CoO2]y has the best overall thermoelectric performance. Compared with the other two cases studied, the full Ca substituted crystal [Bi2Ca2O4][CoO2]y exhibits both reduced resistivity and thermal conductivity, but not a reduced Seebeck coefficient. The enhanced thermoelectric property in [Bi2Ca2O4][CoO2]y is mainly due to lower structural symmetry, which is confirmed by electron microscopy characterization. This work demonstrates that even isovalently substitution can play a crucial role in the thermoelectric effect of layered cobalt oxides.

Substituting Direct Government Lending for Guaranteed Student Loans: How Budget Rules Distorted Economic Decisionmaking.

ERIC Educational Resources Information Center

Zimmerman, Dennis; Miles, Barbara

1994-01-01

Congress substituted direct federal loans for federal guarantee of private loans for postsecondary education. Budget savings were overestimated because credit risks, recognition of administrative costs, and increases in administrative and borrowing costs were ignored. Savings could have been achieved by reducing returns to private lenders and…

Construction of substituted benzene rings by palladium-catalyzed direct cross-coupling of olefins: a rapid synthetic route to 1,4-naphthoquinone and its derivatives.

PubMed

Hu, Peng; Huang, Shijun; Xu, Jing; Shi, Zhang-Jie; Su, Weiping

2011-10-10

Ring the changes: the direct cross-coupling of electron-deficient 1,4-benzoquinone or its derivatives with electron-rich alkyl vinyl ethers proceeds in a tandem manner to produce substituted benzene rings with good selectivity and in good to excellent yields. The reaction has the potential for the rapid synthesis of diverse substituted benzene rings as it is not limited by substituent effects. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a strategy and computational application to select candidate protein analogues with reduced HLA binding and immunogenicity.

PubMed

Dhanda, Sandeep Kumar; Grifoni, Alba; Pham, John; Vaughan, Kerrie; Sidney, John; Peters, Bjoern; Sette, Alessandro

2018-01-01

Unwanted immune responses against protein therapeutics can reduce efficacy or lead to adverse reactions. T-cell responses are key in the development of such responses, and are directed against immunodominant regions within the protein sequence, often associated with binding to several allelic variants of HLA class II molecules (promiscuous binders). Herein, we report a novel computational strategy to predict 'de-immunized' peptides, based on previous studies of erythropoietin protein immunogenicity. This algorithm (or method) first predicts promiscuous binding regions within the target protein sequence and then identifies residue substitutions predicted to reduce HLA binding. Further, this method anticipates the effect of any given substitution on flanking peptides, thereby circumventing the creation of nascent HLA-binding regions. As a proof-of-principle, the algorithm was applied to Vatreptacog α, an engineered Factor VII molecule associated with unintended immunogenicity. The algorithm correctly predicted the two immunogenic peptides containing the engineered residues. As a further validation, we selected and evaluated the immunogenicity of seven substitutions predicted to simultaneously reduce HLA binding for both peptides, five control substitutions with no predicted reduction in HLA-binding capacity, and additional flanking region controls. In vitro immunogenicity was detected in 21·4% of the cultures of peptides predicted to have reduced HLA binding and 11·4% of the flanking regions, compared with 46% for the cultures of the peptides predicted to be immunogenic. This method has been implemented as an interactive application, freely available online at http://tools.iedb.org/deimmunization/. © 2017 John Wiley & Sons Ltd.

3D-QSAR studies on the inhibitory activity of trimethoprim analogues against Escherichia coli dihydrofolate reductase.

PubMed

Vijayaraj, Ramadoss; Devi, Mekapothula Lakshmi Vasavi; Subramanian, Venkatesan; Chattaraj, Pratim Kumar

2012-06-01

Three-dimensional quantitative structure activity relationship (3D-QSAR) study has been carried out on the Escherichia coli DHFR inhibitors 2,4-diamino-5-(substituted-benzyl)pyrimidine derivatives to understand the structural features responsible for the improved potency. To construct highly predictive 3D-QSAR models, comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) methods were used. The predicted models show statistically significant cross-validated and non-cross-validated correlation coefficient of r2 CV and r2 nCV, respectively. The final 3D-QSAR models were validated using structurally diverse test set compounds. Analysis of the contour maps generated from CoMFA and CoMSIA methods reveals that the substitution of electronegative groups at the first and second position along with electropositive group at the third position of R2 substitution significantly increases the potency of the derivatives. The results obtained from the CoMFA and CoMSIA study delineate the substituents on the trimethoprim analogues responsible for the enhanced potency and also provide valuable directions for the design of new trimethoprim analogues with improved affinity. © 2012 John Wiley & Sons A/S.

The use of photographic rates to estimate densities of tigers and other cryptic mammals: a comment on misleading conclusions

USGS Publications Warehouse

Jennelle, C.S.; Runge, M.C.; MacKenzie, D.I.

2002-01-01

The search for easy-to-use indices that substitute for direct estimation of animal density is a common theme in wildlife and conservation science, but one fraught with well-known perils (Nichols & Conroy, 1996; Yoccoz, Nichols & Boulinier, 2001; Pollock et al., 2002). To establish the utility of an index as a substitute for an estimate of density, one must: (1) demonstrate a functional relationship between the index and density that is invariant over the desired scope of inference; (2) calibrate the functional relationship by obtaining independent measures of the index and the animal density; (3) evaluate the precision of the calibration (Diefenbach et al., 1994). Carbone et al. (2001) argue that the number of camera-days per photograph is a useful index of density for large, cryptic, forest-dwelling animals, and proceed to calibrate this index for tigers (Panthera tigris). We agree that a properly calibrated index may be useful for rapid assessments in conservation planning. However, Carbone et al. (2001), who desire to use their index as a substitute for density, do not adequately address the three elements noted above. Thus, we are concerned that others may view their methods as justification for not attempting directly to estimate animal densities, without due regard for the shortcomings of their approach.

Economic aspects of drug substitution

PubMed Central

Salehi, Hossein; Schweitzer, Stuart O.

1985-01-01

One of the major directions of health policy is the attempt to contain expenditures on pharmaceuticals by encouraging substitution of generic for brand name drug products. Yet, a major marketing survey of prescribing and dispensing patterns in California in 1977 found relatively little drug substitution occurring, and in fact substitution of more expensive products occurred more frequently than did substitution of less expensive products. This article tests alternative models of pharmacy dispensing behavior to better explain substitution patterns and it estimates price functions to measure the extent to which cost savings on generic products are passed on to consumers. PMID:10311162

Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation.

PubMed

Chen, G; Wong, P; Cooks, R G

1997-09-01

Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.

Towards a safe non-invasive method for evaluating the carbonate substitution levels of hydroxyapatite (HAP) in micro-calcifications found in breast tissue.

PubMed

Kerssens, Marleen M; Matousek, Pavel; Rogers, Keith; Stone, Nicholas

2010-12-01

A new diagnostic concept based on deep Raman spectroscopy is proposed permitting the non-invasive determination of the level of carbonate substitution in type II calcifications (HAP). The carbonate substitution has shown to be directly associated with the pathology of the surrounding breast tissue and different pathology groups can therefore be separated using specific features in the Raman spectra of the calcifications. This study explores the principle of distinguishing between type II calcifications, found in proliferating lesions, by using the strongest Raman peak from calcium hydroxyapatites (the phosphate peak at 960 cm(-1)) to act as a surrogate marker for carbonate substitution levels. It is believed that carbonate ion substitution leads to a perturbation of the hydroxyapatite lattice which in turn affects the phosphate vibrational modes. By studying calcifications, with known carbonate content, buried in porcine tissue it has been possible to evaluate the feasibility of using the proposed approach to probe the composition of the calcifications in vivo and hence provide pathology specific information non-invasively, in real time. Using the proposed concept we were able to determine the level of carbonate substitutions through soft tissue phantom samples (total thickness of 5.6 mm). As the level of carbonate substitution has been previously correlated with mid-FTIR to the lesion type, i.e. whether benign or invasive or in situ carcinoma, the new findings provide a major step forward towards establishing a new capability for diagnosing benign and malignant lesions in breast tissue in a safe and non-invasive manner in vivo.

The two gap transitions in Ge1 -xSnx : Effect of non-substitutional complex defects

NASA Astrophysics Data System (ADS)

Querales-Flores, J. D.; Ventura, C. I.; Fuhr, J. D.; Barrio, R. A.

2016-09-01

The existence of non-substitutional β-Sn defects in Ge1 -xSnx alloys was confirmed by emission channeling experiments [Decoster et al., Phys. Rev. B 81, 155204 (2010)], which established that, although most Sn enters substitutionally (α-Sn) in the Ge lattice, a second significant fraction corresponds to the Sn-vacancy defect complex in the split-vacancy configuration (β-Sn), in agreement with our previous theoretical study [Ventura et al., Phys. Rev. B 79, 155202 (2009)]. Here, we present the electronic structure calculations for Ge1 -xSnx , including the substitutional α-Sn as well as the non-substitutional β-Sn defects. To include the presence of the non-substitutional complex defects in the electronic structure calculation for this multi-orbital alloy problem, we extended the approach for the purely substitutional alloy by Jenkins and Dow [Phys. Rev. B 36, 7994 (1987)]. We employed an effective substitutional two-site cluster equivalent to the real non-substitutional β-Sn defect, which was determined by a Green's functions calculation. We then calculated the electronic structure of the effective alloy purely in terms of substitutional defects, embedding the effective substitutional clusters in the lattice. Our results describe the two transitions of the fundamental gap of Ge1 -xSnx as a function of the total Sn-concentration: namely, from an indirect to a direct gap, first, and the metallization transition at a higher x. They also highlight the role of β-Sn in the reduction of the concentration range, which corresponds to the direct-gap phase of this alloy of interest for the optoelectronics applications.

Aircraft gas turbine materials and processes.

PubMed

Kear, B H; Thompson, E R

1980-05-23

Materials and processing innovations that have been incorporated into the manufacture of critical components for high-performance aircraft gas turbine engines are described. The materials of interest are the nickel- and cobalt-base superalloys for turbine and burner sections of the engine, and titanium alloys and composites for compressor and fan sections of the engine. Advanced processing methods considered include directional solidification, hot isostatic pressing, superplastic foring, directional recrystallization, and diffusion brazing. Future trends in gas turbine technology are discussed in terms of materials availability, substitution, and further advances in air-cooled hardware.

Chronic Intermittent Ethanol Inhalation Increases Ethanol Self-administration in both C57BL/6J and DBA/2J Mice

PubMed Central

McCool, Brian A.; Chappell, Ann M.

2015-01-01

Inbred mouse strains provide significant opportunities to understand the genetic mechanisms controlling ethanol-directed behaviors and neurobiology. They have been specifically employed to understand cellular mechanisms contributing to ethanol consumption, acute intoxication, and sensitivities to chronic effects. However, limited ethanol consumption by some strains has restricted our understanding of clinically relevant endpoints such as dependence-related ethanol intake. Previous work with a novel tastant-substitution procedure using monosodium glutamate (MSG or umami flavor) has shown that the procedure greatly enhances ethanol consumption by mouse strains that express limited drinking phenotypes using other methods. In the current study, we employ this MSG-substitution procedure to examine how ethanol dependence, induced with passive vapor inhalation, modifies ethanol drinking in C57BL/6J and DBA/2J mice. These strains represent ‘high’ and ‘low’ drinking phenotypes, respectively. We found that the MSG substitution greatly facilitates ethanol drinking in both strains, and likewise, ethanol dependence increased ethanol consumption regardless of strain. However, DBA/2J mice exhibited greater sensitivity dependence-enhanced drinking, as represented by consumption behaviors directed at lower ethanol concentrations and relative to baseline intake levels. DBA/2J mice also exhibited significant withdrawal-associated anxiety-like behavior while C57BL/6J mice did not. These findings suggest that the MSG-substitution procedure can be employed to examine dependence-enhanced ethanol consumption across a range of drinking phenotypes, and that C57BL/6J and DBA/2J mice may represent unique neurobehavioral pathways for developing dependence-enhanced ethanol consumption. PMID:25659650

Comparison of carbohydrate and peptide biotinylation on the immunological activity of IgG1 murine monoclonal antibodies.

PubMed

Miralles, F; Takeda, Y; Escribano, M J

1991-07-05

When the classical amino acid esterification procedure was used for the biotinylation of the IgG1 monoclonal antibody J28 it resulted in a loss of immunological activity. This antibody recognizes the fetoacinar pancreatic (FAP) antigen and the decrease in reactivity was directly proportional to the molar biotin/antibody ratio indicating substitutions at or near the antibody combining site. This effect was specific to J28 since the IgG1 Mab F22 which recognises the same antigen was not damaged by this procedure. Active Mab J28 conjugates were obtained using biotinylation via oligosaccharide moieties. The biotinylation efficiency using this method was dependent on the previous degree of antibody periodate oxidation and the maximal substitution was 3 mol biotin per mol of antibody. Using these conditions the sensitivity of the biotinylated J28 for the FAP antigen was similar to that obtained when using non-substituted antibody in the two antibodies technique.

Electronic Effects of 11β Substituted 17β-Estradiol Derivatives and Instrumental Effects on the Relative Gas Phase Acidity

NASA Astrophysics Data System (ADS)

Bourgoin-Voillard, Sandrine; Fournier, Françoise; Afonso, Carlos; Zins, Emilie-Laure; Jacquot, Yves; Pèpe, Claude; Leclercq, Guy; Tabet, Jean-Claude

2012-12-01

Numerous studies have highlighted the role of the proton donor characteristics of the phenol group of 17β-estradiol (E2) in its association with the estrogen receptor alpha (ERα). Since the substitutions at position C(11) have been reported to modulate this association, we hypothesized that such substitutions may modify the phenol acidity. Hence, phenol gas-phase acidity of nine C(11)-substituted E2-derivatives were evaluated using the extended Cooks' kinetic method, which is a method widely used to determine thermochemical properties by mass spectrometry. To enhance accuracy in data collection we recorded data from several instruments, including quadrupole ion trap, triple quadrupole, and hybrid QqTOF. Indeed, we report for the first time the use of the QqTOF instrument to provide a novel means to improve data accuracy by giving access to an intermediate effective temperature range. All experimental gas-phase acidity values were supported by theoretical calculations. Our results confirmed the ability of distant substituents at C(11) to modulate the phenol acidity through electrostatic interactions, electron withdrawing inductive effects, and mesomeric effects. However, no relationship was found between the phenol gas-phase acidity of investigated steroids and their binding affinity for ERα assessed in solution. Thus, our results highlight that the intrinsic properties of the hormone do not influence sufficiently the stabilization of the hormone/ERα complex. It is more likely that such stabilization would be more related to factors depending on the environment within the binding pocket such as hydrophobic, steric as well as direct intermolecular electrostatic effects between ERα residues and the substituted steroidal estrogens.

Nursing Home Staffing Requirements and Input Substitution: Effects on Housekeeping, Food Service, and Activities Staff

PubMed Central

Bowblis, John R; Hyer, Kathryn

2013-01-01

Objective To study the effect of minimum nurse staffing requirements on the subsequent employment of nursing home support staff. Data Sources Nursing home data from the Online Survey Certification and Reporting (OSCAR) System merged with state nurse staffing requirements. Study Design Facility-level housekeeping, food service, and activities staff levels are regressed on nurse staffing requirements and other controls using fixed effect panel regression. Data Extraction Method OSCAR surveys from 1999 to 2004. Principal Findings Increases in state direct care and licensed nurse staffing requirements are associated with decreases in the staffing levels of all types of support staff. Conclusions Increased nursing home nurse staffing requirements lead to input substitution in the form of reduced support staffing levels. PMID:23445455

Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

PubMed

Evans, P Andrew; Negru, Daniela E; Shang, Deju

2015-04-13

The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pd-catalyzed aerobic oxidative annulation of cyclohexanones and 2-aminophenyl ketones: A direct approach to acridines

NASA Astrophysics Data System (ADS)

Mu, Wanlu; Li, Xiaowei; Wang, Longfei; Chen, Yong; Wu, Yanchao

2017-08-01

An efficient aerobic oxidative annulation of cyclohexanones and 2-aminophenyl ketones approach to substituted acridines, a structural motif for a large number of pharmaceuticals and functional materials is described. The key feature of this method is the use of oxygen as the sole oxidant and Pd catalyst, which resulting in the high regioselectivity with unsymmetrical meta-substituted cyclohexanones. The electron gap of the global redox condensation process is filled and the reaction efficiency is significantly promoted by O2 as a redox moderator. This protocol possesses many advantages such as using O2 as a cheap and nonhazardous oxidant, high regioselectivity and water as the only by-product, which meet the principle of green chemistry.

Protein consensus-based surface engineering (ProCoS): a computer-assisted method for directed protein evolution.

PubMed

Shivange, Amol V; Hoeffken, Hans Wolfgang; Haefner, Stefan; Schwaneberg, Ulrich

2016-12-01

Protein consensus-based surface engineering (ProCoS) is a simple and efficient method for directed protein evolution combining computational analysis and molecular biology tools to engineer protein surfaces. ProCoS is based on the hypothesis that conserved residues originated from a common ancestor and that these residues are crucial for the function of a protein, whereas highly variable regions (situated on the surface of a protein) can be targeted for surface engineering to maximize performance. ProCoS comprises four main steps: ( i ) identification of conserved and highly variable regions; ( ii ) protein sequence design by substituting residues in the highly variable regions, and gene synthesis; ( iii ) in vitro DNA recombination of synthetic genes; and ( iv ) screening for active variants. ProCoS is a simple method for surface mutagenesis in which multiple sequence alignment is used for selection of surface residues based on a structural model. To demonstrate the technique's utility for directed evolution, the surface of a phytase enzyme from Yersinia mollaretii (Ymphytase) was subjected to ProCoS. Screening just 1050 clones from ProCoS engineering-guided mutant libraries yielded an enzyme with 34 amino acid substitutions. The surface-engineered Ymphytase exhibited 3.8-fold higher pH stability (at pH 2.8 for 3 h) and retained 40% of the enzyme's specific activity (400 U/mg) compared with the wild-type Ymphytase. The pH stability might be attributed to a significantly increased (20 percentage points; from 9% to 29%) number of negatively charged amino acids on the surface of the engineered phytase.

Biocatalytic trifluoromethylation of unprotected phenols

NASA Astrophysics Data System (ADS)

Simon, Robert C.; Busto, Eduardo; Richter, Nina; Resch, Verena; Houk, Kendall N.; Kroutil, Wolfgang

2016-11-01

Organofluorine compounds have become important building blocks for a broad range of advanced materials, polymers, agrochemicals, and increasingly for pharmaceuticals. Despite tremendous progress within the area of fluorination chemistry, methods for the direct introduction of fluoroalkyl-groups into organic molecules without prefunctionalization are still highly desired. Here we present a concept for the introduction of the trifluoromethyl group into unprotected phenols by employing a biocatalyst (laccase), tBuOOH, and either the Langlois' reagent or Baran's zinc sulfinate. The method relies on the recombination of two radical species, namely, the phenol radical cation generated directly by the laccase and the CF3-radical. Various functional groups such as ketone, ester, aldehyde, ether and nitrile are tolerated. This laccase-catalysed trifluoromethylation proceeds under mild conditions and allows accessing trifluoromethyl-substituted phenols that were not available by classical methods.

A stochastic evolution model for residue Insertion-Deletion Independent from Substitution.

PubMed

Lèbre, Sophie; Michel, Christian J

2010-12-01

We develop here a new class of stochastic models of gene evolution based on residue Insertion-Deletion Independent from Substitution (IDIS). Indeed, in contrast to all existing evolution models, insertions and deletions are modeled here by a concept in population dynamics. Therefore, they are not only independent from each other, but also independent from the substitution process. After a separate stochastic analysis of the substitution and the insertion-deletion processes, we obtain a matrix differential equation combining these two processes defining the IDIS model. By deriving a general solution, we give an analytical expression of the residue occurrence probability at evolution time t as a function of a substitution rate matrix, an insertion rate vector, a deletion rate and an initial residue probability vector. Various mathematical properties of the IDIS model in relation with time t are derived: time scale, time step, time inversion and sequence length. Particular expressions of the nucleotide occurrence probability at time t are given for classical substitution rate matrices in various biological contexts: equal insertion rate, insertion-deletion only and substitution only. All these expressions can be directly used for biological evolutionary applications. The IDIS model shows a strongly different stochastic behavior from the classical substitution only model when compared on a gene dataset. Indeed, by considering three processes of residue insertion, deletion and substitution independently from each other, it allows a more realistic representation of gene evolution and opens new directions and applications in this research field. Copyright © 2010 Elsevier Ltd. All rights reserved.

Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.

PubMed

Souza, Frederico B; Shamim, Anwar; Argomedo, Luiz M Z; Pimenta, Daniel C; Stefani, Hélio A

2015-11-01

An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement.

Substituent Effects in the Benzene Dimer are Due to Direct Interactions of the Substituents with the Unsubstituted Benzene

PubMed Central

Wheeler, Steven E.; Houk, K. N.

2009-01-01

The prevailing views of substituent effects in the sandwich configuration of the benzene dimer are flawed. For example, in the polar/π model of Cozzi and co-workers (J. Am. Chem. Soc. 1992, 114, 5729), electron-withdrawing substituents enhance binding in the benzene dimer by withdrawing electron density from the π-cloud of the substituted ring, reducing the repulsive electrostatic interaction with the non-substituted benzene. Conversely, electron-donating substituents donate excess electrons into the π-system and diminish the π-stacking interaction. We present computed interaction energies for the sandwich configuration of the benzene dimer and 24 substituted dimers, as well as sandwich complexes of substituted benzenes with perfluorobenzene. While the computed interaction energies correlate well with σm values for the substituents, interaction energies for related model systems demonstrate that this trend is independent of the substituted ring. Instead, the observed trends are consistent with direct electrostatic and dispersive interactions of the substituents with the unsubstituted ring. PMID:18652453

A Web service substitution method based on service cluster nets

NASA Astrophysics Data System (ADS)

Du, YuYue; Gai, JunJing; Zhou, MengChu

2017-11-01

Service substitution is an important research topic in the fields of Web services and service-oriented computing. This work presents a novel method to analyse and substitute Web services. A new concept, called a Service Cluster Net Unit, is proposed based on Web service clusters. A service cluster is converted into a Service Cluster Net Unit. Then it is used to analyse whether the services in the cluster can satisfy some service requests. Meanwhile, the substitution methods of an atomic service and a composite service are proposed. The correctness of the proposed method is proved, and the effectiveness is shown and compared with the state-of-the-art method via an experiment. It can be readily applied to e-commerce service substitution to meet the business automation needs.

Amino acid substitutions in the hepatitis C virus core region predict hepatocarcinogenesis following eradication of HCV RNA by all-oral direct-acting antiviral regimens.

PubMed

Ogata, Fumihiro; Akuta, Norio; Kobayashi, Masahiro; Fujiyama, Shunichiro; Kawamura, Yusuke; Sezaki, Hitomi; Hosaka, Tetsuya; Kobayashi, Mariko; Saitoh, Satoshi; Suzuki, Yoshiyuki; Suzuki, Fumitaka; Arase, Yasuji; Ikeda, Kenji; Kumada, Hiromitsu

2018-06-01

Impact of substitution of aa70 in the core region (Core aa70) in HCV genotype 1b (HCV-1b) on hepatocarcinogenesis following eradication of HCV RNA by direct-acting antiviral therapy is not clear. In a retrospective study, 533 patients with HCV-related chronic liver disease, with sustained virological response defined as negative HCV RNA at 12 weeks after cessation of direct-acting antiviral therapy, were examined to evaluate the relationship between Core aa70 substitution and hepatocarcinogenesis. Twelve patients developed hepatocellular carcinoma during the follow-up period. The cumulative hepatocarcinogenesis rates were 1.7% and 2.4% at the end of 1 and 2 years, respectively. Overall, multivariate analysis identified HCV subgroup (HCV-1b with Gln70(His70); P = 0.003) and age (>65 years; P = 0.049), as pretreatment predictors of hepatocarcinogenesis. In HCV-1b patients, multivariate analysis identified post-treatment Wisteria floribunda agglutinin positive Mac-2 binding protein (>1.8 COI; P = 0.042) and HCV subgroup (HCV-1b with Gln70(His70); P = 0.071), as predictors of hepatocarcinogenesis, including post-treatment parameter. In conclusion, Core aa70 substitution in HCV-1b at the start of direct-acting antiviral therapy is an important predictor of hepatocarcinogenesis following eradication of HCV RNA. This study emphasizes the importance of detection of Core aa70 substitution before initiating antiviral therapy. © 2018 Wiley Periodicals, Inc.

Methods for preparation of cyclopentadienyliron (II) arenes

DOEpatents

Keipert, Steven J.

1991-01-01

Two improved methods for preparation of compounds with the structure shown in equation X [(Cp)--Fe--(Ar)].sup.+.sub.b X.sup.b- (X) where Cp is an eta.sup.5 complexed, substituted or unsubstituted, cyclopentadienyl or indenyl anion, Ar is an eta.sup.6 complexed substituted or unsubstituted, pi-arene ligand anad X is a b-valent anion where b is an integer between 1 and 3. The two methods, which differ in the source of the cyclopentadienyl anion - Lewis acid complex, utilize a Lewis acid assisted ligand transfer reaction. The cyclopentadienyl anion ligand, assisted by a Lewis acid is transferred to ferrous ion in the presence of an arene. In the first method, the cyclopentadienyl anion is derived from ferrocene and ferrous chloride. In this reaction, the cyclopentadienyliron (II) arene product is derived partially from ferrocene and partially from the ferrous salt. In the second method, the cyclopentadienyl anion - Lewis acid complex is formed by direct reaction of the Lewis acid with an inorganic cyclopentadienide salt. The cyclopentadienyliron (II) arene product of this reaction is derived entirely from the ferrous salt. Cyclopentadienyliron (II) arene cations are of great interest due to their utility as photoactivatable catalysts for a variety of polymerization reactions.

Sample preparation of metal alloys by electric discharge machining

NASA Technical Reports Server (NTRS)

Chapman, G. B., II; Gordon, W. A.

1976-01-01

Electric discharge machining was investigated as a noncontaminating method of comminuting alloys for subsequent chemical analysis. Particulate dispersions in water were produced from bulk alloys at a rate of about 5 mg/min by using a commercially available machining instrument. The utility of this approach was demonstrated by results obtained when acidified dispersions were substituted for true acid solutions in an established spectrochemical method. The analysis results were not significantly different for the two sample forms. Particle size measurements and preliminary results from other spectrochemical methods which require direct aspiration of liquid into flame or plasma sources are reported.

Characterisation of the ester-substituted products of the reaction of p-t-butyl calix[4]arene and ethyl bromoacetate using LC-UV-MS and LC-DAD.

PubMed

McMahon, Gillian; Wall, Rachel; Nolan, Kieran; Diamond, Dermot

2002-07-19

A series of derivatisation reactions between p-t-butyl calix[4]arene and ethyl bromoacetate were carried out in order to prepare 1,3 diester substituted calix[4]arene. Mass spectral data, obtained from direct injection of samples, indicated that the reactions were rich in the desired product. Since the ultra violet (UV) spectra of the desired product and possible impurities are very similar, liquid chromatography (LC) chromatographic data seemed to corroborate these results. However, when on-line LC-UV-MS was carried out and each LC peak subjected to MS analysis as it eluted, a very different picture emerged. It was found that many of these reactions actually contained high levels of the monoester product which, having less affinity for sodium in the MS, is therefore seriously underestimated in any direct injection assay. LC-diode array detection (DAD) methods were also used to help successfully identify and characterise the compounds being formed in these complex reactions. The overall results obtained in this paper allowed the optimal reaction conditions to be determined for this reaction. LC-MS analysis of the chromatographic peaks also identified the presence of two isomers of the diester substituted calix[4]arene (1,3 and 1,2 diesters). The combination of LC and UV/MS detection is required for accurate analysis of the products of such reactions.

Equivalent-Continuum Modeling With Application to Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Gates, Thomas S.; Nicholson, Lee M.; Wise, Kristopher E.

2002-01-01

A method has been proposed for developing structure-property relationships of nano-structured materials. This method serves as a link between computational chemistry and solid mechanics by substituting discrete molecular structures with equivalent-continuum models. It has been shown that this substitution may be accomplished by equating the vibrational potential energy of a nano-structured material with the strain energy of representative truss and continuum models. As important examples with direct application to the development and characterization of single-walled carbon nanotubes and the design of nanotube-based devices, the modeling technique has been applied to determine the effective-continuum geometry and bending rigidity of a graphene sheet. A representative volume element of the chemical structure of graphene has been substituted with equivalent-truss and equivalent continuum models. As a result, an effective thickness of the continuum model has been determined. This effective thickness has been shown to be significantly larger than the interatomic spacing of graphite. The effective thickness has been shown to be significantly larger than the inter-planar spacing of graphite. The effective bending rigidity of the equivalent-continuum model of a graphene sheet was determined by equating the vibrational potential energy of the molecular model of a graphene sheet subjected to cylindrical bending with the strain energy of an equivalent continuum plate subjected to cylindrical bending.

First detection of multiple knockdown resistance (kdr)-like mutations in voltage-gated sodium channel using three new genotyping methods in Anopheles sinensis from Guangxi Province, China.

PubMed

Tan, Wei L; Li, Chun X; Wang, Zhong M; Liu, Mei D; Dong, Yan D; Feng, Xiang Y; Wu, Zhi M; Guo, Xiao X; Xing, Dan; Zhang, Ying M; Wang, Zhong C; Zhao, Tong Y

2012-09-01

To investigate knockdown resistance (kdr)-like mutations associated with pyrethroid resistance in Anopheles sinensis (Wiedemann, 1828), from Guangxi province, southwest China, a segment of a sodium channel gene was sequenced and genotyped using three new genotyping assays. Direct sequencing revealed the presence of TTG-to-TCG and TG-to-TTT mutations at allele position L1014, which led to L1014S and L1014F substitutions in a few individual and two novel substitutions of N1013S and L1014W in two DNA templates. A low frequency of the kdr allele mostly in the heterozygous state of L1014S and L1014F was observed in this mosquito population. In this study, the genotyping of An. sinensis using three polymerase chain reaction-based methods generated consistent results, which agreed with the results of DNA sequencing. In total, 52 mosquitoes were genotyped using a direct sequencing assay. The number of mosquitoes and their genotypes were as follows: L/L = 24, L/S = 19, L/F = 8, and F/W = 1. The allelic frequency of L1014, 1014S, and 1014F were 72, 18, and 9%, respectively.

Sequencing of hepatitis C virus for detection of resistance to direct-acting antiviral therapy: A systematic review.

PubMed

Bartlett, Sofia R; Grebely, Jason; Eltahla, Auda A; Reeves, Jacqueline D; Howe, Anita Y M; Miller, Veronica; Ceccherini-Silberstein, Francesca; Bull, Rowena A; Douglas, Mark W; Dore, Gregory J; Harrington, Patrick; Lloyd, Andrew R; Jacka, Brendan; Matthews, Gail V; Wang, Gary P; Pawlotsky, Jean-Michel; Feld, Jordan J; Schinkel, Janke; Garcia, Federico; Lennerstrand, Johan; Applegate, Tanya L

2017-07-01

The significance of the clinical impact of direct-acting antiviral (DAA) resistance-associated substitutions (RASs) in hepatitis C virus (HCV) on treatment failure is unclear. No standardized methods or guidelines for detection of DAA RASs in HCV exist. To facilitate further evaluations of the impact of DAA RASs in HCV, we conducted a systematic review of RAS sequencing protocols, compiled a comprehensive public library of sequencing primers, and provided expert guidance on the most appropriate methods to screen and identify RASs. The development of standardized RAS sequencing protocols is complicated due to a high genetic variability and the need for genotype- and subtype-specific protocols for multiple regions. We have identified several limitations of the available methods and have highlighted areas requiring further research and development. The development, validation, and sharing of standardized methods for all genotypes and subtypes should be a priority. ( Hepatology Communications 2017;1:379-390).

Stampless fabrication of sheet bars using disposable templates

NASA Astrophysics Data System (ADS)

Smolentsev, V. P.; Safonov, S. V.; Smolentsev, E. V.; Fedonin, O. N.

2016-04-01

The article is devoted to the new method of small-scale fabrication of sheet bars. The procedure is performed by using disposable overlay templates, or those associated with a sheet, which parameters are obtained directly from the drawing. The proposed method used as a substitution of die cutting enables to intensify the preparatory technological process, which is particularly effective when launching the market-oriented items into production. It significantly increases the competitiveness of mechanical engineering and creates the conditions for technical support of present-day flexible production systems.

Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn(2-x)M(x)Te3O8 (M = Co, Ni, Cu).

PubMed

Tamilarasan, S; Sarma, Debajit; Bhattacharjee, S; Waghmare, U V; Natarajan, S; Gopalakrishnan, J

2013-05-20

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal-substituted spiroffite derivatives, Zn(2-x)M(x)Te3O8 (M(II) = Co, Ni, Cu; 0 < x ≤ 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 °C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M(II)-O bonds (1.898-2.236 Å) and one longer Zn/M(II)-O bond (2.356-2.519 Å). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn(2-x)M(x)Te3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M(II)-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M(II) = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn(2-x)M(x)Te3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

Chronic intermittent ethanol inhalation increases ethanol self-administration in both C57BL/6J and DBA/2J mice.

PubMed

McCool, Brian A; Chappell, Ann M

2015-03-01

Inbred mouse strains provide significant opportunities to understand the genetic mechanisms controlling ethanol-directed behaviors and neurobiology. They have been specifically employed to understand cellular mechanisms contributing to ethanol consumption, acute intoxication, and sensitivities to chronic effects. However, limited ethanol consumption by some strains has restricted our understanding of clinically relevant endpoints such as dependence-related ethanol intake. Previous work with a novel tastant-substitution procedure using monosodium glutamate (MSG or umami flavor) has shown that the procedure greatly enhances ethanol consumption by mouse strains that express limited drinking phenotypes using other methods. In the current study, we employ this MSG-substitution procedure to examine how ethanol dependence, induced with passive vapor inhalation, modifies ethanol drinking in C57BL/6J and DBA/2J mice. These strains represent 'high' and 'low' drinking phenotypes, respectively. We found that the MSG substitution greatly facilitates ethanol drinking in both strains, and likewise, ethanol dependence increased ethanol consumption regardless of strain. However, DBA/2J mice exhibited greater sensitivity dependence-enhanced drinking, as represented by consumption behaviors directed at lower ethanol concentrations and relative to baseline intake levels. DBA/2J mice also exhibited significant withdrawal-associated anxiety-like behavior while C57BL/6J mice did not. These findings suggest that the MSG-substitution procedure can be employed to examine dependence-enhanced ethanol consumption across a range of drinking phenotypes, and that C57BL/6J and DBA/2J mice may represent unique neurobehavioral pathways for developing dependence-enhanced ethanol consumption. Copyright © 2015 Elsevier Inc. All rights reserved.

Microneedle crystals of cyano-substituted thiophene/phenylene co-oligomer epitaxially grown on KCl surface

NASA Astrophysics Data System (ADS)

Torii, Kazuki; Dokiya, Shohei; Tanaka, Yosuke; Yoshinaga, Shohei; Yanagi, Hisao

2017-06-01

A cyno-substituted thiophene/phenylene co-oligomer (TPCO), 5,5‧-bis(4‧-cyanobiphenyl-4-yl)-2,2‧-bithiophene (BP2T-CN), is vapor-deposited on KCl (001) surface kept at 220 °C by the mask-shadowing method. Transmission electron microscopy and fluorescence microscopy reveal that the deposited BP2T-CN crystallizes in two types of morphologies: microneedles and thin film crystallites. In particular, the predominant microneedles epitaxially grow in four directions in the manner that the BP2T-CN molecules align along the [110]KCl or [-110]KCl. X-ray diffraction patterns indicate that the BP2T-CN molecules in the microneedle lie parallel while those in the thin film crystallite obliquely stand on the KCl surface.

Structural diversification of the aminobicyclo[4.3.0]nonane skeleton using alkynylsilyl-derived allylic trichloroacetimidates.

PubMed

Mostafa, Mohamed A B; McMillan, Angus E; Sutherland, Andrew

2017-04-05

The amino substituted bicyclo[4.3.0]nonane is a molecular scaffold found in a wide range of natural products and medicinal agents. Despite this, synthetic methods for the general preparation of this structural motif are sparse. Here we evaluate a diastereoselective approach for the preparation of vinylsilyl derived aminobicyclo[4.3.0]nonanes using a one-pot multi-bond forming process involving a Pd(ii)-catalysed Overman rearrangement, a Ru(ii)-catalysed ring closing enyne metathesis reaction, followed by a hydrogen bonding directed Diels-Alder reaction. We show that a benzyldimethylsilyl-substituted alkene analogue is amenable to further functionalisation and the late stage generation of diverse sp 3 -rich, drug-like aminobicyclo[4.3.0]nonane scaffolds with up to six stereogenic centres.

Biocatalytic trifluoromethylation of unprotected phenols

PubMed Central

Simon, Robert C.; Busto, Eduardo; Richter, Nina; Resch, Verena; Houk, Kendall N.; Kroutil, Wolfgang

2016-01-01

Organofluorine compounds have become important building blocks for a broad range of advanced materials, polymers, agrochemicals, and increasingly for pharmaceuticals. Despite tremendous progress within the area of fluorination chemistry, methods for the direct introduction of fluoroalkyl-groups into organic molecules without prefunctionalization are still highly desired. Here we present a concept for the introduction of the trifluoromethyl group into unprotected phenols by employing a biocatalyst (laccase), tBuOOH, and either the Langlois' reagent or Baran's zinc sulfinate. The method relies on the recombination of two radical species, namely, the phenol radical cation generated directly by the laccase and the CF3-radical. Various functional groups such as ketone, ester, aldehyde, ether and nitrile are tolerated. This laccase-catalysed trifluoromethylation proceeds under mild conditions and allows accessing trifluoromethyl-substituted phenols that were not available by classical methods. PMID:27834376

Single genome retrieval of context-dependent variability in mutation rates for human germline.

PubMed

Sahakyan, Aleksandr B; Balasubramanian, Shankar

2017-01-13

Accurate knowledge of the core components of substitution rates is of vital importance to understand genome evolution and dynamics. By performing a single-genome and direct analysis of 39,894 retrotransposon remnants, we reveal sequence context-dependent germline nucleotide substitution rates for the human genome. The rates are characterised through rate constants in a time-domain, and are made available through a dedicated program (Trek) and a stand-alone database. Due to the nature of the method design and the imposed stringency criteria, we expect our rate constants to be good estimates for the rates of spontaneous mutations. Benefiting from such data, we study the short-range nucleotide (up to 7-mer) organisation and the germline basal substitution propensity (BSP) profile of the human genome; characterise novel, CpG-independent, substitution prone and resistant motifs; confirm a decreased tendency of moieties with low BSP to undergo somatic mutations in a number of cancer types; and, produce a Trek-based estimate of the overall mutation rate in human. The extended set of rate constants we report may enrich our resources and help advance our understanding of genome dynamics and evolution, with possible implications for the role of spontaneous mutations in the emergence of pathological genotypes and neutral evolution of proteomes.

Tissue engineered constructs for peripheral nerve surgery

PubMed Central

Johnson, P. J.; Wood, M. D.; Moore, A. M.; Mackinnon, S. E.

2013-01-01

Summary Background Tissue engineering has been defined as “an interdisciplinary field that applies the principles of engineering and life sciences toward the development of biological substitutes that restore, maintain, or improve tissue function or a whole organ”. Traumatic peripheral nerve injury resulting in significant tissue loss at the zone of injury necessitates the need for a bridge or scaffold for regenerating axons from the proximal stump to reach the distal stump. Methods A review of the literature was used to provide information on the components necessary for the development of a tissue engineered peripheral nerve substitute. Then, a comprehensive review of the literature is presented composed of the studies devoted to this goal. Results Extensive research has been directed toward the development of a tissue engineered peripheral nerve substitute to act as a bridge for regenerating axons from the proximal nerve stump seeking the distal nerve. Ideally this nerve substitute would consist of a scaffold component that mimics the extracellular matrix of the peripheral nerve and a cellular component that serves to stimulate and support regenerating peripheral nerve axons. Conclusions The field of tissue engineering should consider its challenge to not only meet the autograft “gold standard” but also to understand what drives and inhibits nerve regeneration in order to surpass the results of an autograft. PMID:24385980

[Guidelines for substitution treatments in prison populations].

PubMed

Michel, L; Maguet, O

2005-01-01

Care access for the drug addict patients in prison (in particular for the treatments of substitution) in France is very unequal from one establishment to another. This reflects the great variability of the practices of substitution and especially the absence of consensus on the methods of adaptation of these practices to the prison environment. Because of difficulties expressed by prisoners and medical staff on this subject and of stakes (let us recall that approximately 30% of the prisoners are dependent or abusers of one or more psychoactive substances), the formulation of recommendations or of a good practices guide of substitution in prison appeared necessary. Work that we detail here answers a ordering of the Advisory Commission of the Treatments of Substitution (September 2001) whose authors are members. It was presented at the session April 2003. It results from the confrontation of a review of the literature (including legal texts and official reports concerning substitution, the organization of the care in prison environment and the lawful framework), with a vast investigation. The latter was carried out near medical staff (22 prisons), penitentiary staff (3 prisons, 27 people met including directors of these establishments) and prisoners (7 establishments, 28 prisoners met) in the form of individual talks (semi-directing interviews with evaluation of the type of existing device and its knowledge by the penitentiary staff and the prisoners; statement of the suggestions, needs and requests of the medical, penitentiary staffs and of the prisoners). In the whole visited prisons, 7.8% (870) of the prisoners received substitution treatments (6.35% by buprenorphine, 1.44% by methadone), representing a proportion of substituted drug addicts (870 substituted for an evaluation of 3,350 prisoners drug addicts among the 11,168 prisoners of the 22 visited prisons) notably lower than that in free environment (56%, ie 96,000 substituted for an evaluated population of drug addicts for heroin of 160,000). There are however considerable variations (from 0 to 16.2%) of the proportion of substituted of one establishment for the other according to the type of prison, of its size, its localization and the type of medical device present. If a consensus exists for methadone (daily delivery with sanitary control), the organization of the care relating to the buprenorphine is extremely variable from one establishment to another, often putting in difficulty as well the medical teams as the prisoners. One recommendation is essential: the formulation of an individualized therapeutic project. Thirteen other recommendations are made in the following fields: renewal of substitution treatments, initiation of substitution treatments, urinary controls, methods of prescription, methods of delivery, co-prescriptions, global care, confidentiality, files, exits and transfers, extractions, formation, accompaniment of the teams. These recommendations being formulated, many medical concerns remain present and several questions open. The report of joint mission IGAS/IGSJ of June 2001 on the health of the prisoners underlines the principal persistent gaps: hygiene and public health, treatment of the mental disorders, the follow-up of the sexual delinquents, handling ageing, handicap and the end of lifetime. In the same way, the difficulties listed in prison environment concerning substitution are only the exacerbation of those existing outside: the misuses and traffics are common in free environment, risk reduction in prison, as outside, handle with obstacles related to the penalization of the drug use and can hardly evolve except questioning the law of 1970. The prison practice opens also questions: that of the "duration" of the substitution, frequently posed by the prisoners; concern to see the prison becoming a privileged place of access to the care, combining sanction and care whereas the law of 1970 allows the alternative (care or sanction); that of the clinic of the misuse, particularly "readable" in prison environment; and finally the question of the shared secrecy, extremely delicate in prison context although clarified by the law of March 04, 2002.

2H and 27Al solid-state NMR study of the local environments in Al-doped 2-line ferrihydrite, goethite, and lepidocrocite

DOE PAGES

Kim, Jongsik; Ilott, Andrew J.; Middlemiss, Derek S.; ...

2015-05-13

Although substitution of aluminum into iron oxides and oxyhydroxides has been extensively studied, it is difficult to obtain accurate incorporation levels. Assessing the distribution of dopants within these materials has proven especially challenging because bulk analytical techniques cannot typically determine whether dopants are substituted directly into the bulk iron oxide or oxyhydroxide phase or if they form separate, minor phase impurities. These differences have important implications for the chemistry of these iron-containing materials, which are ubiquitous in the environment. In this work, 27Al and 2H NMR experiments are performed on series of Al-substituted goethite, lepidocrocite, and 2-line ferrihydrite in ordermore » to develop an NMR method to track Al substitution. The extent of Al substitution into the structural frameworks of each compound is quantified by comparing quantitative 27Al MAS NMR results with those from elemental analysis. Magnetic measurements are performed for the goethite series to compare with NMR measurements. Static 27Al spin–echo mapping experiments are used to probe the local environments around the Al substituents, providing clear evidence that they are incorporated into the bulk iron phases. As a result, predictions of the 2H and 27Al NMR hyperfine contact shifts in Al-doped goethite and lepidocrocite, obtained from a combined first-principles and empirical magnetic scaling approach, give further insight into the distribution of the dopants within these phases.« less

Trans beta substituted chlorins and methods of making and using the same

DOEpatents

Lindsey, Jonathan S.; Balasubramanian, Thiagarajan

2003-05-06

Trans beta substituted chlorins and methods of making the same are disclosed, along with polymers formed from or containing such trans beta substituted chlorins as one or more monomeric units therein, light harvesting rods formed from such polymers, and electrodes carrying such polymers.

Ionic liquids comprising heteraromatic anions

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

Schneider, William F.; Brennecke, Joan F.; Maginn, Edward J.

2018-04-24

Some embodiments described herein relate to ionic liquids comprising an anion of a heteraromatic compound such as optionally substituted pyrrolide, optionally substituted pyrazolide, optionally substituted indolide, optionally substituted phospholide, or optionally substituted imidazolide. Methods and devices for gas separation or gas absorption related to these ionic liquids are also described herein.

Functionalized polyfluorenes for use in optoelectronic devices

DOEpatents

Chichak, Kelly Scott [Clifton Park, NY; Lewis, Larry Neil [Scotia, NY; Cella, James Anthony [Clifton Park, NY; Shiang, Joseph John [Niskayuna, NY

2011-11-08

The present invention relates to process comprising reacting a polyfluorenes comprising at least one structural group of formula I ##STR00001## with an iridium (III) compound of formula II ##STR00002## wherein R.sup.1 and R.sup.2 are independently alkyl, substituted alkyl, aryl, substituted aryl or a combination thereof; R.sup.5is H or CHO; R.sup.3 and R.sup.4 are independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl or a combination thereof; R.sup.11 and R.sup.12 taken together form a substituted or unsubstituted monocyclic or bicyclic heteroaromatic ring; R.sup.13 is independently at each occurrence halo, nitro, hydroxy, amino, alkyl, aryl, arylalkyl, alkoxy, substituted alkoxy, substituted alkyl, substituted aryl, or substituted arylalkyl; Ar is aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a combination thereof; X is selected from a direct bond, alky, substituted alkyl, and combinations thereof; Y is CHO or NH.sub.2; Z is CHO or NH.sub.2 where Z does not equal Y; and p is 0, 1 or 2. The invention also relates to the polyfluorenes, which are products of the reaction, and the use of the polyfluorenes in optoelectronic devices.

Cu substituted CeCo 5 : New optimal permanent magnetic material with reduced criticality

DOE PAGES

Chouhan, Rajiv K.; Paudyal, D.

2017-06-26

A comprehensive theoretical prediction using a mechanism of site substitution confirms the crucial role of Cu in enhancing the capabilities of CeCo 5 as a competitive magnet with its known high coercivity. A remarkable enhancement of magnetic anisotropy energy (MAE) of 3.09 meV/f.u. and 2.94 meV/f.u. without significant decrease of magnetic moment is found for 10% and 5% Cu substitution at 2c sites of the hexagonal lattice. Our calculations predict the increment of coercivity and magnetocrystalline anisotropy (1.6 times) compared to pristine CeCo 5. Furthermore, the exceptional enhancement in MAE is due to the formation of asymmetric charge hybridization amongmore » the Cu (2c) and Co (both 2c and 3g) sites along the uniaxial direction. Because of this asymmetric charge distribution environment, the intrinsic behavior of Ce adjacent to Cu changes abruptly making them more uniaxial and magnetically enhanced creating mixed valence states. For our calculations, we have employed the full-potential augmented plane wave method in conjunction with spin orbit coupling.« less

Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters.

PubMed

Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su

2014-05-16

A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

A Facile Preparation of Imidazolinium Chlorides

PubMed Central

Kuhn, Kevin M.; Grubbs, Robert H.

2009-01-01

A process for the preparation of symmetric and unsymmetric imidazolinium chlorides that involves reaction of a formamidine with dichloroethane and a base (a) is described. This method makes it possible to obtain numerous imidazolinium chlorides under solvent-free reaction conditions and in excellent yields with purification by simple filtration. Alternatively, symmetric imidazolinium chlorides can be prepared directly in moderate yields from substituted anilines by utilizing half of the formamidine intermediate as sacrificial base (b). PMID:18412354

Precision Assembly of Systems on Surfaces (PASS)

DTIC Science & Technology

2015-02-06

As a result, under other funding we are pursuing applications of this method for the detection of biogenic amines that are indicators of meat ...conductive materials are made from indium tin oxide or fluorinated tin oxide. The latter involves the substitution of a F- for an O-2 and leads to n...generated by spoiling meat . Our fully drawn sensors and ability to fabricate materials on many substrates has assisted us in ongoing experiments directed

Polybenzimidazole compounds, polymeric media, and methods of post-polymerization modifications

DOEpatents

Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.; Jones, Michael G.; Wertsching, Alan K.; Luther, Thomas A.; Trowbridge, Tammy L.

2007-12-18

A PBI compound includes imidazole nitrogens at least a portion of which are substituted with a moiety containing a carbonyl group, the substituted imidazole nitrogens being bonded to carbon of the carbonyl group. At least 85% of the nitrogens may be substituted. The carbonyl-containing moiety may include RCO--, where R is alkoxy or haloalkyl. The PBI compound may exhibit a first temperature marking an onset of weight loss corresponding to reversion of the substituted PBI that is less than a second temperature marking an onset of decomposition of an otherwise identical PBI compound without the substituted moiety. The PBI compound may be included in separatory media. A substituted PBI synthesis method may include providing a parent PBI in a less than 5 wt % solvent solution. Substituting may use more than 5 equivalents in relation to the imidazole nitrogens to be substituted.

Evaluation of methods for managing censored results when calculating the geometric mean.

PubMed

Mikkonen, Hannah G; Clarke, Bradley O; Dasika, Raghava; Wallis, Christian J; Reichman, Suzie M

2018-01-01

Currently, there are conflicting views on the best statistical methods for managing censored environmental data. The method commonly applied by environmental science researchers and professionals is to substitute half the limit of reporting for derivation of summary statistics. This approach has been criticised by some researchers, raising questions around the interpretation of historical scientific data. This study evaluated four complete soil datasets, at three levels of simulated censorship, to test the accuracy of a range of censored data management methods for calculation of the geometric mean. The methods assessed included removal of censored results, substitution of a fixed value (near zero, half the limit of reporting and the limit of reporting), substitution by nearest neighbour imputation, maximum likelihood estimation, regression on order substitution and Kaplan-Meier/survival analysis. This is the first time such a comprehensive range of censored data management methods have been applied to assess the accuracy of calculation of the geometric mean. The results of this study show that, for describing the geometric mean, the simple method of substitution of half the limit of reporting is comparable or more accurate than alternative censored data management methods, including nearest neighbour imputation methods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Directed differentiation of embryonic stem cells using a bead-based combinatorial screening method.

PubMed

Tarunina, Marina; Hernandez, Diana; Johnson, Christopher J; Rybtsov, Stanislav; Ramathas, Vidya; Jeyakumar, Mylvaganam; Watson, Thomas; Hook, Lilian; Medvinsky, Alexander; Mason, Chris; Choo, Yen

2014-01-01

We have developed a rapid, bead-based combinatorial screening method to determine optimal combinations of variables that direct stem cell differentiation to produce known or novel cell types having pre-determined characteristics. Here we describe three experiments comprising stepwise exposure of mouse or human embryonic cells to 10,000 combinations of serum-free differentiation media, through which we discovered multiple novel, efficient and robust protocols to generate a number of specific hematopoietic and neural lineages. We further demonstrate that the technology can be used to optimize existing protocols in order to substitute costly growth factors with bioactive small molecules and/or increase cell yield, and to identify in vitro conditions for the production of rare developmental intermediates such as an embryonic lymphoid progenitor cell that has not previously been reported.

Are private physicians more likely to veto generic substitution of prescribed pharmaceuticals?

PubMed

Granlund, David

2009-12-01

Physicians' decisions whether or not to veto generic substitution were analyzed using a sample of 350,000 pharmaceutical prescriptions from the county of Västerbotten, Sweden. Although generic substitution reforms have been introduced in many European countries and American states, this is to my knowledge the first study on this topic. The topic is important since physicians' decisions regarding generic substitution not only directly affect patients' and insurers' costs for pharmaceuticals, but also indirectly since more bans against substitution reduces price-competition between pharmaceutical firms. The primary purpose was to test if physicians working at private practices were more likely to oppose substitution than county-employed physicians working on salary. It was found that private physicians were 50-80% more likely to veto substitution. Also, the probability of a veto was found to increase as patients' copayments decreased. This might indicate moral hazard in insurance, though other explanations are plausible.

Nonenzymatic oligomerization reactions on templates containing inosinic acid or diaminopurine nucleotide residues

NASA Technical Reports Server (NTRS)

Kozlov, I. A.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

1999-01-01

The template-directed oligomerization of nucleoside-5'-phosphoro-2-methyl imidazolides on standard oligonucleotide templates has been studied extensively. Here, we describe experiments with templates in which inosinic acid (I) is substituted for guanylic acid, or 2,6-diaminopurine nucleotide (D) for adenylic acid. We find that the substitution of I for G in a template is strongly inhibitory and prevents any incorporation of C into internal positions in the oligomeric products of the reaction. The substitution of D for A, on the contrary, leads to increased incorporation of U into the products. We found no evidence for the template-directed facilitation of oligomerization of A or I through A-I base pairing. The significance of these results for prebiotic chemistry is discussed.

12 CFR 167.1 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-01-01

... institution. The term domestic depository institution means a financial institution that engages in the... substitute. Direct credit substitutes include: (1) Financial standby letters of credit that support financial claims on a third party that exceed a savings association's pro rata share in the financial claim; (2...

12 CFR 167.1 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

... institution. The term domestic depository institution means a financial institution that engages in the... substitute. Direct credit substitutes include: (1) Financial standby letters of credit that support financial claims on a third party that exceed a savings association's pro rata share in the financial claim; (2...

12 CFR 167.1 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

... institution. The term domestic depository institution means a financial institution that engages in the... substitute. Direct credit substitutes include: (1) Financial standby letters of credit that support financial claims on a third party that exceed a savings association's pro rata share in the financial claim; (2...

Biomimetic heterogenous elastic tissue development.

PubMed

Tsai, Kai Jen; Dixon, Simon; Hale, Luke Richard; Darbyshire, Arnold; Martin, Daniel; de Mel, Achala

2017-01-01

There is an unmet need for artificial tissue to address current limitations with donor organs and problems with donor site morbidity. Despite the success with sophisticated tissue engineering endeavours, which employ cells as building blocks, they are limited to dedicated labs suitable for cell culture, with associated high costs and long tissue maturation times before available for clinical use. Direct 3D printing presents rapid, bespoke, acellular solutions for skull and bone repair or replacement, and can potentially address the need for elastic tissue, which is a major constituent of smooth muscle, cartilage, ligaments and connective tissue that support organs. Thermoplastic polyurethanes are one of the most versatile elastomeric polymers. Their segmented block copolymeric nature, comprising of hard and soft segments allows for an almost limitless potential to control physical properties and mechanical behaviour. Here we show direct 3D printing of biocompatible thermoplastic polyurethanes with Fused Deposition Modelling, with a view to presenting cell independent in-situ tissue substitutes. This method can expeditiously and economically produce heterogenous, biomimetic elastic tissue substitutes with controlled porosity to potentially facilitate vascularisation. The flexibility of this application is shown here with tubular constructs as exemplars. We demonstrate how these 3D printed constructs can be post-processed to incorporate bioactive molecules. This efficacious strategy, when combined with the privileges of digital healthcare, can be used to produce bespoke elastic tissue substitutes in-situ, independent of extensive cell culture and may be developed as a point-of-care therapy approach.

The Electronic and Optical Properties of Au Doped Single-Layer Phosphorene

NASA Astrophysics Data System (ADS)

Zhu, Ziqing; Chen, Changpeng; Liu, Jiayi; Han, Lu

2018-01-01

The electronic properties and optical properties of single and double Au-doped phosphorene have been comparatively investigated using the first-principles plane-wave pseudopotential method based on density functional theory. The decrease from direct band gap 0.78 eV to indirect band gap 0.22 and 0.11 eV are observed in the single and double Au-doped phosphorene, respectively. The red shifts of absorbing edge occur in both doped systems, which consequently enhance the absorbing of infrared light in phosphorene. Band gap engineering can, therefore, be used to directly tune the optical absorption of phosphorene system by substitutional Au doping.

Statistical properties of the Jukes-Holmquist method of estimating the number of nucleotide substitutions: reply to Holmquist and Conroy's criticism.

PubMed

Nei, M; Tateno, Y

1981-01-01

Conducting computer simulations, Nei and Tateno (1978) have shown that Jukes and Holmquist's (1972) method of estimating the number of nucleotide substitutions tends to give an overestimate and the estimate obtained has a large variance. Holmquist and Conroy (1980) repeated some parts of our simulation and claim that the overestimation of nucleotide substitutions in our paper occurred mainly because we used selected data. Examination of Holmquist and Conroy's simulation indicates that their results are essentially the same as ours when the Jukes-Holmquist method is used, but since they used a different method of computation their estimates of nucleotide substitutions differed substantially from ours. Another problem in Holmquist and Conroy's Letter is that they confused the expected number of nucleotide substitution with the number in a sample. This confusion has resulted in a number of unnecessary arguments. They also criticized our X2 measure, but this criticism is apparently due to a misunderstanding of the assumptions of our method and a failure to use our method in the way we described. We believe that our earlier conclusions remain unchanged.

Directed evolution for thermostabilization of a hygromycin B phosphotransferase from Streptomyces hygroscopicus.

PubMed

Sugimoto, Naohisa; Takakura, Yasuaki; Shiraki, Kentaro; Honda, Shinya; Takaya, Naoki; Hoshino, Takayuki; Nakamura, Akira

2013-01-01

To obtain a selection marker gene functional in a thermophilic bacterium, Thermus thermophilus, an in vivo-directed evolutionary strategy was conducted on a hygromycin B phosphotransferase gene (hyg) from Streptomyces hygroscopicus. The expression of wild-type hyg in T. thermophilus provided hygromycin B (HygB) resistance up to 60 °C. Through selection of mutants showing HygB resistance at higher temperatures, eight amino acid substitutions and the duplication of three amino acids were identified. A variant containing seven substitutions and the duplication (HYG10) showed HygB resistance at a highest temperature of 74 °C. Biochemical and biophysical analyses of recombinant HYG and HYG10 revealed that HYG10 was in fact thermostabilized. Modeling of the three-dimensional structure of HYG10 suggests the possible roles of the various substitutions and the duplication on thermostabilization, of which three substitutions and the duplication located at the enzyme surface suggested that these mutations made the enzyme more hydrophilic and provided increased stability in aqueous solution.

Evolution and dispersal of St. Louis encephalitis virus in the Americas.

PubMed

Auguste, Albert J; Pybus, Oliver G; Carrington, Christine V F

2009-07-01

Using a Bayesian coalescent approach on a dataset of 73 envelope gene sequences we estimated substitution rates and dates of divergence for St. Louis encephalitis virus (SLEV) in the Americas. We found significant rate heterogeneity among lineages, such that "relaxed" molecular clock models were much better supported than a strict molecular clock. The mean substitution rate estimated for all SLEV was 4.1x10(-4)substitutions/site/year (95% HPD 2.5-5.7)-higher than previous estimates that relied on the less well-suited strict clock. Mean substitution rates for individual lineages varied from 3.7x10(-4) to 7.2x10(-4)substitutions/site/year. For the first time we also assessed the magnitude and direction of viral gene flow within the Americas. The overall direction of gene flow during the period represented by the phylogeny is from South to North, and the region between 15 degrees N and 30 degrees N latitude appears to be the major source of virus for the rest of North America, which is consistent with migratory birds returning to their northern breeding grounds having acquired infection while wintering in the region of the Gulf of Mexico.

Neural Correlates of Direct and Indirect Suppression of Autobiographical Memories

PubMed Central

Noreen, Saima; O’Connor, Akira R.; MacLeod, Malcolm D.

2016-01-01

Research indicates that there are two possible mechanisms by which particular target memories can be intentionally forgotten. Direct suppression, which involves the suppression of the unwanted memory directly, and is dependent on a fronto-hippocampal modulatory process, and, memory substitution, which includes directing one’s attention to an alternative memory in order to prevent the unwanted memory from coming to mind, and involves engaging the caudal prefrontal cortex (cPFC) and the mid-ventrolateral prefrontal cortex (VLPFC) regions. Research to date, however, has investigated the neural basis of memory suppression of relatively simple information. The aim of the current study was to use fMRI to identify the neural mechanisms associated with the suppression of autobiographical memories. In the present study, 22 participants generated memories in response to a series of cue words. In a second session, participants learnt these cue-memory pairings, and were subsequently presented with a cue word and asked either to recall (think) or to suppress (no-think) the associated memory, or to think of an alternative memory in order to suppress the original memory (memory-substitution). Our findings demonstrated successful forgetting effects in the no-think and memory substitution conditions. Although we found no activation in the dorsolateral prefrontal cortex, there was reduced hippocampal activation during direct suppression. In the memory substitution condition, however, we failed to find increased activation in the cPFC and VLPFC regions. Our findings suggest that the suppression of autobiographical memories may rely on different neural mechanisms to those established for other types of material in memory. PMID:27047412

Neural Correlates of Direct and Indirect Suppression of Autobiographical Memories.

PubMed

Noreen, Saima; O'Connor, Akira R; MacLeod, Malcolm D

2016-01-01

Research indicates that there are two possible mechanisms by which particular target memories can be intentionally forgotten. Direct suppression, which involves the suppression of the unwanted memory directly, and is dependent on a fronto-hippocampal modulatory process, and, memory substitution, which includes directing one's attention to an alternative memory in order to prevent the unwanted memory from coming to mind, and involves engaging the caudal prefrontal cortex (cPFC) and the mid-ventrolateral prefrontal cortex (VLPFC) regions. Research to date, however, has investigated the neural basis of memory suppression of relatively simple information. The aim of the current study was to use fMRI to identify the neural mechanisms associated with the suppression of autobiographical memories. In the present study, 22 participants generated memories in response to a series of cue words. In a second session, participants learnt these cue-memory pairings, and were subsequently presented with a cue word and asked either to recall (think) or to suppress (no-think) the associated memory, or to think of an alternative memory in order to suppress the original memory (memory-substitution). Our findings demonstrated successful forgetting effects in the no-think and memory substitution conditions. Although we found no activation in the dorsolateral prefrontal cortex, there was reduced hippocampal activation during direct suppression. In the memory substitution condition, however, we failed to find increased activation in the cPFC and VLPFC regions. Our findings suggest that the suppression of autobiographical memories may rely on different neural mechanisms to those established for other types of material in memory.

Chromatographic methods for determination of S-substituted cysteine derivatives--a comparative study.

PubMed

Kubec, Roman; Dadáková, Eva

2009-10-09

A novel HPLC method for determination of a wide variety of S-substituted cysteine derivatives in Allium species has been developed and validated. This method allows simultaneous separation and quantification of S-alk(en)ylcysteine S-oxides, gamma-glutamyl-S-alk(en)ylcysteines and gamma-glutamyl-S-alk(en)ylcysteine S-oxides in a single run. The procedure is based on extraction of these amino acids and dipeptides by methanol, their derivatization by dansyl chloride and subsequent separation by reversed phase HPLC. The main advantages of the new method are simplicity, excellent stability of derivatives, high sensitivity, specificity and the ability to simultaneously analyze the whole range of S-substituted cysteine derivatives. This method was critically compared with other chromatographic procedures used for quantification of S-substituted cysteine derivatives, namely with two other HPLC methods (derivatization by o-phthaldialdehyde/tert-butylthiol and fluorenylmethyl chloroformate), and with determination by gas chromatography or capillary electrophoresis. Major advantages and drawbacks of these analytical procedures are discussed. Employing these various chromatographic methods, the content and relative proportions of individual S-substituted cysteine derivatives were determined in four most frequently consumed alliaceous vegetables (garlic, onion, shallot, and leek).

Crystal growth and piezoelectric properties of Ca3Ta(Ga0.9Sc0.1)3Si2O14 bulk single crystal

NASA Astrophysics Data System (ADS)

Igarashi, Yu; Yokota, Yuui; Ohashi, Yuji; Inoue, Kenji; Yamaji, Akihiro; Shoji, Yasuhiro; Kamada, Kei; Kurosawa, Shunsuke; Yoshikawa, Akira

2018-03-01

Ca3Ta(Ga0.9Sc0.1)3Si2O14 langasite-type single crystal with a diameter of 1 in. was grown by Czochralski (Cz) method. Obtained crystal had good crystallinity and its lattice constants exceeded those of Ca3TaGa3Si2O14 (CTGS) according to the X-ray analysis. A crack-free specimen cut from the grown crystal was used for the measurements of dielectric constant ε11T/ε0, electromechanical coupling factor k12, and piezoelectric constant d11. The accuracies of these measurements were better than those for the crystal grown by micro-pulling-down (μ-PD) method. Substitution of Ga with Sc resulted modification of these constants in the directions opposite to those observed after partial substitution of Ga (of CTGS) with Al. This suggests that increase of |d14| was most probably associated with enlargement of average size of the Ga sites. The crystal reported here had greater dimensions as compared to analogous crystals grown by the μ-PD method. As a result, accuracy of determination of acoustic constants of this material may be improved.

Laser spectrometer for CO2 clumped isotope analysis

NASA Astrophysics Data System (ADS)

Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

2017-04-01

Carbon dioxide clumped isotope thermometry has proven to be a reliable method for biogeochemical and atmospheric research. We present a new laser spectroscopic instrument for doubly-substituted isotopologues analysis. In contrast to a conventional isotope ratio mass spectrometry (IRMS), tunable laser direct absorption spectroscopy (TLDAS) has the advantage of isotopologue-specific determination free of isobaric interferences. Tunable infrared laser based spectrometer for clumped isotope analysis is being developed in collaboration between Heidelberg University, Germany, and LERMA-IPSL, CNRS, France. The instrument employs two continuous intraband cascade lasers (ICL) tuned at 4439 and 4329 nm. The spectral windows covered by the lasers contain absorption lines of the six most abundant CO2 isotopologues, including the two doubly substituted species 16O13C18O and 16O13C17O, and all singly substituted isotopologues with 13C, 18O and 17O. A Herriott-type multi-pass cell provides two different absorption pathlengths to compensate the abundance difference between singly- and doubly-substituted isotopologues. We have reached the sub-permill precision required for clumped isotope measurements within the integration time of several seconds. The test version of the instrument demonstrates a performance comparable to state of the art IRMS. We highlight the following features of the instrument that are strong advantages compared to conventional mass spectrometry: measurement cycle in the minute range, simplified sample preparation routine, table-top layout with a potential for in-situ applications.

Synthesis and first-principle calculations of the structural and electronic properties of Ge-substituted type-VIII Ba8Ga16Sn30 clathrate

NASA Astrophysics Data System (ADS)

Shen, Lanxian; Li, Decong; Liu, Hongxia; Liu, Zuming; Deng, Shukang

2016-12-01

In this study, the structural and electronic structural properties of Ba8Ga16Sn30-xGex (0≤x≤30) are determined by the first-principle method on the basis of density functional theory. Consistent with experimental findings, calculated results reveal that Ge atoms preferentially occupy the 2a and 24g sites in these compounds. As the content of Ge in Ge-substituted clathrate is increased, the lattice parameter is decreased, and the structural stability is enhanced. The bandgaps of the compound at 1≤x≤10 are smaller than those of Ba8Ga16Sn30. By contrast, the bandgaps of the compound at x>10 are larger than those of Ba8Ga16Sn30. The substitution of Ge for Sn affects p-type conductivity but not n-type conductivity. As Ge content increases, the whole conduction band moves to the direction of high energy, and the density of states of valence-band top decreases. The calculated potential energy versus displacement of Ba indicates that the vibration energy of this atom increases as cage size decreases. Because Ge substitution also affects clathrate structural symmetry, the distance of Ba atom deviation from the center of the cage initially increases and subsequently decreases as the Ge content increases.

Evaluation of the energy budget method of determining evaporation at Williams Lake, Minnesota, using alternative instrumentation and study approaches

USGS Publications Warehouse

Rosenberry, D.O.; Sturrock, A.M.; Winter, T.C.

1993-01-01

Best estimates of evaporation at Williams Lake, north central Minnesota, were determined by the energy budget method using optimum sensors and optimum placement of sensors. These best estimates are compared with estimates derived from using substitute data to determine the effect of using less accurate sensors, simpler methods, or remotely measured data. Calculations were made for approximately biweekly periods during five open water seasons. For most of the data substitutions that affected the Bowen ratio, new values of evaporation differed little from best estimates. The three data substitution methods that caused the largest deviations from the best evaporation estimates were (1) using changes in the daily average surface water temperature as an indicator of the lake heat storage term, (2) using shortwave radiation, air temperature, and atmospheric vapor pressure data from a site 110 km away, and (3) using an analog surface water temperature probe. Recalculations based on these data substitutions resulted in differences from the best estimates as much as 89%, 21%, and 10%, respectively. The data substitution method that provided evaporation values that most closely matched the best estimates was measurement of the lake heat storage term at one location in the lake, rather than at 16 locations. Evaporation values resulting from this substitution method usually were within 2% of the best estimates.

Synthesis of substituted pyrazines

DOEpatents

Pagoria, Philip F.; Zhang, Mao Xi

2016-10-04

A method for synthesizing a pyrazine-containing material according to one embodiment includes contacting an iminodiacetonitrile derivative with a base and a reagent selected from a group consisting of hydroxylamine, a hydroxylamine salt, an aliphatic primary amine, a secondary amine, an aryl-substituted alkylamine a heteroaryl-substituted alkyl amine, an alcohol, an alkanolamine and an aryl alcoholamine. Additional methods and several reaction products are presented. ##STR00001##

Wavefront reconstruction for multi-lateral shearing interferometry using difference Zernike polynomials fitting

NASA Astrophysics Data System (ADS)

Liu, Ke; Wang, Jiannian; Wang, Hai; Li, Yanqiu

2018-07-01

For the multi-lateral shearing interferometers (multi-LSIs), the measurement accuracy can be enhanced by estimating the wavefront under test with the multidirectional phase information encoded in the shearing interferogram. Usually the multi-LSIs reconstruct the test wavefront from the phase derivatives in multiple directions using the discrete Fourier transforms (DFT) method, which is only suitable to small shear ratios and relatively sensitive to noise. To improve the accuracy of multi-LSIs, wavefront reconstruction from the multidirectional phase differences using the difference Zernike polynomials fitting (DZPF) method is proposed in this paper. For the DZPF method applied in the quadriwave LSI, difference Zernike polynomials in only two orthogonal shear directions are required to represent the phase differences in multiple shear directions. In this way, the test wavefront can be reconstructed from the phase differences in multiple shear directions using a noise-variance weighted least-squares method with almost no extra computational burden, compared with the usual recovery from the phase differences in two orthogonal directions. Numerical simulation results show that the DZPF method can maintain high reconstruction accuracy in a wider range of shear ratios and has much better anti-noise performance than the DFT method. A null test experiment of the quadriwave LSI has been conducted and the experimental results show that the measurement accuracy of the quadriwave LSI can be improved from 0.0054 λ rms to 0.0029 λ rms (λ = 632.8 nm) by substituting the DFT method with the proposed DZPF method in the wavefront reconstruction process.

Directed Differentiation of Embryonic Stem Cells Using a Bead-Based Combinatorial Screening Method

PubMed Central

Tarunina, Marina; Hernandez, Diana; Johnson, Christopher J.; Rybtsov, Stanislav; Ramathas, Vidya; Jeyakumar, Mylvaganam; Watson, Thomas; Hook, Lilian; Medvinsky, Alexander; Mason, Chris; Choo, Yen

2014-01-01

We have developed a rapid, bead-based combinatorial screening method to determine optimal combinations of variables that direct stem cell differentiation to produce known or novel cell types having pre-determined characteristics. Here we describe three experiments comprising stepwise exposure of mouse or human embryonic cells to 10,000 combinations of serum-free differentiation media, through which we discovered multiple novel, efficient and robust protocols to generate a number of specific hematopoietic and neural lineages. We further demonstrate that the technology can be used to optimize existing protocols in order to substitute costly growth factors with bioactive small molecules and/or increase cell yield, and to identify in vitro conditions for the production of rare developmental intermediates such as an embryonic lymphoid progenitor cell that has not previously been reported. PMID:25251366

12 CFR Appendix C to Part 704 - Risk-Based Capital Credit Risk-Weight Categories

Code of Federal Regulations, 2011 CFR

2011-01-01

... corporate credit union must compute its risk-weighted assets for purposes of determining its capital ratios.... Depository institution means a financial institution that engages in the business of providing financial... substitute. Direct credit substitutes include: (1) Financial standby letters of credit that support financial...

21 CFR 184.1259 - Cocoa butter substitute.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Cocoa butter substitute. 184.1259 Section 184.1259 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as...

Determination of polyadipates migrating from lid gaskets of glass jars. Hydrolysis to adipic acid and measurement by LC-MS/MS.

PubMed

Driffield, M; Bradley, E L; Harmer, N; Castle, L; Klump, S; Mottier, P

2010-10-01

Polyadipate plasticizers can be present in the polyvinylchloride (PVC) gaskets used to seal the lids of glass jars. As the gaskets can come into direct contact with the foodstuffs inside the jar, the potential exists for polyadipate migration into the food. The procedure and performance characteristics of a test method for the analysis of polyadipates in food simulants (3% aqueous acetic acid and 10% aqueous ethanol) and the volatile test media used in substitute fat tests (isooctane and 95% aqueous ethanol) are described. The PVC gaskets were exposed to the food simulants or their substitutes under standard test conditions. Studies were initially carried out using direct measurement of the polyadipate oligomers by liquid chromatography with time-of-flight mass spectrometric detection (LC-TOF-MS) but this was not practical due to the number of peaks detected. Instead, the migrating polyadipates were hydrolysed to adipic acid and measured by liquid chromatography with tandem mass spectrometric detection (LC-MS/MS). The amount of polyadipate that this measurement of adipic acid represents was then calculated. Method performance was assessed by analysis of gaskets from two types of jar lids by single-laboratory validation. Linearity, sensitivity, repeatability, intermediate reproducibility and recovery were determined to be suitable for checking compliance with the 30 mg/kg specific migration limits for polyesters of 1,2-propane diol and/or 1,3- and/or 1,4-butanediol and/or polypropylene-glycol with adipic acid, which may be end-capped with acetic acid or fatty acids C(12)-C(18) or n-octanol and/or n-decanol. The method was found to be much quicker than previous methods involving extraction, clean-up, hydrolysis, esterification, derivatisation and GC measurement, consequently saving time and money.

Utility of transthoracic echocardiography (TTE) in assessing fluid responsiveness in critically ill patients - a challenge for the bedside sonographer.

PubMed

Mielnicki, Wojciech; Dyla, Agnieszka; Zawada, Tomasz

2016-12-05

Transthoracic echocardiography (TTE) has become one of the most important diagnostic tools in the treatment of critically ill patients. It allows clinicians to recognise potentially reversible life-threatening situations and is also very effective in the monitoring of the fluid status of patients, slowly substituting invasive methods in the intensive care unit. Hemodynamic assessment is based on a few static and dynamic parameters. Dynamic parameters change during the respiratory cycle in mechanical ventilation and the level of this change directly corresponds to fluid responsiveness. Most of the parameters cannot be used in spontaneously breathing patients. For these patients the most important test is passive leg raising, which is a good substitute for fluid bolus. Although TTE is very useful in the critical care setting, we should not forget the important limitations, not only technical ones but also caused by the critical illness itself. Unfortunately, this method does not allow continuous monitoring and every change in the patient's condition requires repeated examination.

Multiplex PCR method for use in real-time PCR for identification of fish fillets from grouper (Epinephelus and Mycteroperca species) and common substitute species.

PubMed

Trotta, Michele; Schönhuth, Susana; Pepe, Tiziana; Cortesi, M Luisa; Puyet, Antonio; Bautista, José M

2005-03-23

Mitochondrial 16S rRNA sequences from morphological validated grouper (Epinephelus aeneus, E. caninus, E. costae, and E. marginatus; Mycteroperca fusca and M. rubra), Nile perch (Lates niloticus), and wreck fish (Polyprion americanus) were used to develop an analytical system for group diagnosis based on two alternative Polymerase Chain Reaction (PCR) approaches. The first includes conventional multiplex PCR in which electrophoretic migration of different sizes of bands allowed identification of the fish species. The second approach, involving real-time PCR, produced a single amplicon from each species that showed different Tm values allowing the fish groups to be directly identified. Real-time PCR allows the quick differential diagnosis of the three groups of species and high-throughput screening of multiple samples. Neither PCR system cross-reacted with DNA samples from 41 common marketed fish species, thus conforming to standards for species validation. The use of these two PCR-based methods makes it now possible to discriminate grouper from substitute fish species.

A fast direct method for block triangular Toeplitz-like with tri-diagonal block systems from time-fractional partial differential equations

NASA Astrophysics Data System (ADS)

Ke, Rihuan; Ng, Michael K.; Sun, Hai-Wei

2015-12-01

In this paper, we study the block lower triangular Toeplitz-like with tri-diagonal blocks system which arises from the time-fractional partial differential equation. Existing fast numerical solver (e.g., fast approximate inversion method) cannot handle such linear system as the main diagonal blocks are different. The main contribution of this paper is to propose a fast direct method for solving this linear system, and to illustrate that the proposed method is much faster than the classical block forward substitution method for solving this linear system. Our idea is based on the divide-and-conquer strategy and together with the fast Fourier transforms for calculating Toeplitz matrix-vector multiplication. The complexity needs O (MNlog2 ⁡ M) arithmetic operations, where M is the number of blocks (the number of time steps) in the system and N is the size (number of spatial grid points) of each block. Numerical examples from the finite difference discretization of time-fractional partial differential equations are also given to demonstrate the efficiency of the proposed method.

Amino Acid Substitutions in PB1 of Avian Influenza Viruses Influence Pathogenicity and Transmissibility in Chickens

PubMed Central

Suzuki, Yasushi; Uchida, Yuko; Tanikawa, Taichiro; Maeda, Naohiro; Takemae, Nobuhiro

2014-01-01

ABSTRACT Amino acid substitutions were introduced into avian influenza virus PB1 in order to characterize the interaction between polymerase activity and pathogenicity. Previously, we used recombinant viruses containing the hemagglutinin (HA) and neuraminidase (NA) genes from the highly pathogenic avian influenza virus (HPAIV) H5N1 strain and other internal genes from two low-pathogenicity avian influenza viruses isolated from chicken and wild-bird hosts (LP and WB, respectively) to demonstrate that the pathogenicity of highly pathogenic avian influenza viruses (HPAIVs) of subtype H5N1 in chickens is regulated by the PB1 gene (Y. Uchida et al., J. Virol. 86:2686–2695, 2012, doi:http://dx.doi.org/10.1128/JVI.06374-11). In the present study, we introduced a C38Y substitution into WB PB1 and demonstrated that this substitution increased both polymerase activity in DF-1 cells in vitro and the pathogenicity of the recombinant viruses in chickens. The V14A substitution in LP PB1 reduced polymerase activity but did not affect pathogenicity in chickens. Interestingly, the V14A substitution reduced viral shedding and transmissibility. These studies demonstrate that increased polymerase activity correlates directly with enhanced pathogenicity, while decreased polymerase activity does not always correlate with pathogenicity and requires further analysis. IMPORTANCE We identified 2 novel amino acid substitutions in the avian influenza virus PB1 gene that affect the characteristics of highly pathogenic avian influenza viruses (HPAIVs) of the H5N1 subtype, such as viral replication and polymerase activity in vitro and pathogenicity and transmissibly in chickens. An amino acid substitution at residue 38 in PB1 directly affected pathogenicity in chickens and was associated with changes in polymerase activity in vitro. A substitution at residue 14 reduced polymerase activity in vitro, while its effects on pathogenicity and transmissibility depended on the constellation of internal genes. PMID:25031333

Influence of dopant substitution mechanism on catalytic properties within hierarchical architectures

PubMed Central

Newland, Stephanie H.; Sinkler, Wharton; Mezza, Thomas; Bare, Simon R.

2016-01-01

A range of hierarchically porous (HP) AlPO-5 catalysts, with isomorphously substituted transition metal ions, have been synthesized using an organosilane as a soft template. By employing a range of structural and spectroscopic characterization protocols, the properties of the dopant-substituted species within the HP architectures have been carefully evaluated. The resulting nature of the active site is shown to have a direct impact on the ensuing catalytic properties in the liquid-phase Beckmann rearrangement of cyclic ketones. PMID:27493563

Influence of dopant substitution mechanism on catalytic properties within hierarchical architectures

NASA Astrophysics Data System (ADS)

Newland, Stephanie H.; Sinkler, Wharton; Mezza, Thomas; Bare, Simon R.; Raja, Robert

2016-07-01

A range of hierarchically porous (HP) AlPO-5 catalysts, with isomorphously substituted transition metal ions, have been synthesized using an organosilane as a soft template. By employing a range of structural and spectroscopic characterization protocols, the properties of the dopant-substituted species within the HP architectures have been carefully evaluated. The resulting nature of the active site is shown to have a direct impact on the ensuing catalytic properties in the liquid-phase Beckmann rearrangement of cyclic ketones.

Gadolinium substitution effect on the thermomagnetic properties of Ni ferrite ferrofluids

NASA Astrophysics Data System (ADS)

Jacobo, Silvia E.; Arana, Mercedes; Bercoff, Paula G.

2016-10-01

This work is focused on the structural and magnetic characterization of Gd-doped Ni ferrite nanoparticles and the preparation of a ferrofluid for applications in heat-transfer devices. For this purpose, spinel ferrites NiFe2O4, and NiFe1.88Gd0.12O4 were prepared by the self-combustion method. The substituted sample was obtained with a small amount of Gd inclusion and the excess appeared as GdFeO3. The smallest nanoparticles of both samples were properly coated and dispersed in kerosene. Thermal conductivities of the produced ferrofluids were measured at 25 °C under an applied magnetic field. There is a significant enhancement in the thermal conductivity of the ferrofluid prepared with NiGd ferrite with respect to the one with Ni ferrite, in presence of a magnetic field. This effect is directly related to the well-known magnetocaloric effect of Gd.

Structure/Function Analyses of Human Serum Paraoxonase (HuPON1) Mutants Designed from a DFPase-Like Homology Model

DTIC Science & Technology

2004-08-23

purified HuPON1 Substitution of amino acid residues in the HuPONI enzyme was accomplished by PCR-based site-directed Two methods were utilized to...including organophosphates and lactones, and exhibits anti-atherogenic properties. A few amino acids have been shown to be essential for the enzyme’s...not been assigned to those residues. Based on scquence-structure alignment studies, we have folded the amino acid sequence of HuPON I onto the sixfold

Substituted dipyrromethanes and their preparation

DOEpatents

Wijesekera, T.

1997-02-04

New chemical compounds, bis(pyrrol-2-yl)halocarbylmethanes, also known as meso-halocarbyl dipyrromethanes, are made by reacting pyrrole in either of two reaction schemes. One such scheme converts pyrrole through an intermediate, a halocarbyl carbonyl pyrrole, to a [2-(1-hydroxyl-1-hydro1-halocarbyl)pyrrole], and then converts the latter to the desired halocarbyldipyrromethane; the last step in this scheme is a novel and useful method in itself. The other such sequence converts pyrrole, by reaction with a halocarbyl aldehyde, directly to the desired halocarbyl dipyrromethane.

Substituted dipyrromethanes and their preparation

DOEpatents

Wijesekera, T.

1996-03-26

New chemical compounds, bis(pyrrol-2-yl)halocarbylmethanes, also known as meso-halocarbyl dipyrromethanes, are made by reacting pyrrole in either of two reaction schemes. One such scheme converts pyrrole through an intermediate, a halocarbyl carbonyl pyrrole, to a [2-(1-hydroxyl-1-hydro-1-halocarbyl)pyrrole], and then converts the latter to the desired halocarbyldipyrromethane; the last step in this scheme is a novel and useful method in itself. The other such sequence converts pyrrole, by reaction with a halocarbyl aldehyde, directly to the desired halocarbyl dipyrromethane.

Substituted dipyrromethanes and their preparation

DOEpatents

Wijesekera, T.

1996-07-16

New chemical compounds, bis(pyrrol-2-yl)halocarbylmethanes, also known as meso-halocarbyl dipyrromethanes, are made by reacting pyrrole in either of two reaction schemes. One such scheme converts pyrrole through an intermediate, a halocarbyl carbonyl pyrrole, to a [2-(1-hydroxyl-1-hydro1-halocarbyl)pyrrole], and then converts the latter to the desired halocarbyldipyrromethane; the last step in this scheme is a novel and useful method in itself. The other such sequence converts pyrrole, by reaction with a halocarbyl aldehyde, directly to the desired halocarbyl dipyrromethane.

Substituted dipyrromethanes and their preparation

DOEpatents

Wijesekera, Tilak

1996-01-01

New chemical compounds, bis(pyrrol-2-yl)halocarbylmethanes, also known as meso-halocarbyl dipyrromethanes, are made by recting pyrrole in either of two reaction schemes. Once such scheme converts pyrrole through an intermediate, a halocarbyl carbonyl pyrrole, to a [2-(1-hydroxyl-1-hydro-1-halocarbyl)pyrrole], and then converts the latter to the desired halocarbyldipyrromethane; the last step in this scheme is a novel and useful method in itself. The other such sequence converts pyrrole, by reaction with a halocarbyl aldehyde, directly to the desired halocarbyl dipyrromethane.

Substituted dipyrromethanes and their preparation

DOEpatents

Wijesekera, Tilak

1996-01-01

New chemical compounds, bis(pyrrol-2-yl)halocarbylmethanes, also known as meso-halocarbyl dipyrromethanes, are made by recting pyrrole in either of two reaction schemes. Once such scheme converts pyrrole through an intermediate, a halocarbyl carbonyl pyrrole, to a 2-(1-hydroxyl-1-hydro-1-halocarbyl)pyrrole!, and then converts the latter to the desired halocarbyldipyrromethane; the last step in this scheme is a novel and useful method in itself. The other such sequence converts pyrrole, by reaction with a halocarbyl aldehyde, directly to the desired halocarbyl dipyrromethane.

Substituted dipyrromethanes and their preparation

DOEpatents

Wijesekera, Tilak

1997-01-01

New chemical compounds, bis(pyrrol-2-yl)halocarbylmethanes, also known as meso-halocarbyl dipyrromethanes, are made by recting pyrrole in either of two reaction schemes. Once such scheme converts pyrrole through an intermediate, a halocarbyl carbonyl pyrrole, to a [2-(1-hydroxyl-1-hydro-1-halocarbyl)pyrrole], and then converts the latter to the desired halocarbyldipyrromethane; the last step in this scheme is a novel and useful method in itself. The other such sequence converts pyrrole, by reaction with a halocarbyl aldehyde, directly to the desired halocarbyl dipyrromethane.

Metallic conduction induced by direct anion site doping in layered SnSe2

PubMed Central

Kim, Sang Il; Hwang, Sungwoo; Kim, Se Yun; Lee, Woo-Jin; Jung, Doh Won; Moon, Kyoung-Seok; Park, Hee Jung; Cho, Young-Jin; Cho, Yong-Hee; Kim, Jung-Hwa; Yun, Dong-Jin; Lee, Kyu Hyoung; Han, In-taek; Lee, Kimoon; Sohn, Yoonchul

2016-01-01

The emergence of metallic conduction in layered dichalcogenide semiconductor materials by chemical doping is one of key issues for two-dimensional (2D) materials engineering. At present, doping methods for layered dichalcogenide materials have been limited to an ion intercalation between layer units or electrostatic carrier doping by electrical bias owing to the absence of appropriate substitutional dopant for increasing the carrier concentration. Here, we report the occurrence of metallic conduction in the layered dichalcogenide of SnSe2 by the direct Se-site doping with Cl as a shallow electron donor. The total carrier concentration up to ~1020 cm−3 is achieved by Cl substitutional doping, resulting in the improved conductivity value of ~170 S·cm−1 from ~1.7 S·cm−1 for non-doped SnSe2. When the carrier concentration exceeds ~1019 cm−3, the conduction mechanism is changed from hopping to degenerate conduction, exhibiting metal-insulator transition behavior. Detailed band structure calculation reveals that the hybridized s-p orbital from Sn 5s and Se 4p states is responsible for the degenerate metallic conduction in electron-doped SnSe2. PMID:26792630

Metallic conduction induced by direct anion site doping in layered SnSe2.

PubMed

Kim, Sang Il; Hwang, Sungwoo; Kim, Se Yun; Lee, Woo-Jin; Jung, Doh Won; Moon, Kyoung-Seok; Park, Hee Jung; Cho, Young-Jin; Cho, Yong-Hee; Kim, Jung-Hwa; Yun, Dong-Jin; Lee, Kyu Hyoung; Han, In-taek; Lee, Kimoon; Sohn, Yoonchul

2016-01-21

The emergence of metallic conduction in layered dichalcogenide semiconductor materials by chemical doping is one of key issues for two-dimensional (2D) materials engineering. At present, doping methods for layered dichalcogenide materials have been limited to an ion intercalation between layer units or electrostatic carrier doping by electrical bias owing to the absence of appropriate substitutional dopant for increasing the carrier concentration. Here, we report the occurrence of metallic conduction in the layered dichalcogenide of SnSe2 by the direct Se-site doping with Cl as a shallow electron donor. The total carrier concentration up to ~10(20) cm(-3) is achieved by Cl substitutional doping, resulting in the improved conductivity value of ~170 S · cm(-1) from ~1.7 S · cm(-1) for non-doped SnSe2. When the carrier concentration exceeds ~10(19) cm(-3), the conduction mechanism is changed from hopping to degenerate conduction, exhibiting metal-insulator transition behavior. Detailed band structure calculation reveals that the hybridized s-p orbital from Sn 5s and Se 4p states is responsible for the degenerate metallic conduction in electron-doped SnSe2.

Immobilization of magnetic nanoparticles onto conductive surfaces modified by diazonium chemistry.

PubMed

Ktari, Nadia; Quinson, Jonathan; Teste, Bruno; Siaugue, Jean-Michel; Kanoufi, Frédéric; Combellas, Catherine

2012-08-28

Core-shell γ-Fe(2)O(3)@SiO(2) nanoparticles (NPs) substituted by PEG and NH(2) groups may be immobilized on metal surfaces (glassy carbon or gold) substituted by 4-carboxyphenyl groups through electrostatic interactions. Such immobilization is evidenced by (i) IRRAS owing to the Si-O band, (ii) SEM images, which show that the surface coverage by the NPs is nearly 100%, and (iii) the NPs film thickness measured by ellipsometry or AFM, which corresponds to about one NPs monolayer. Such NPs film is permeable to redox probes, which allows us to propose electrochemical methods based on direct or local measurements as a way to inspect the NPs assembly steps through their ability to alter mass and charge transfer. This process also applies to patterned polystyrene surfaces, and selective immobilization of NPs substituted by amino groups was carried out onto submillimeter patterns obtained by local oxidation. Biological applications are then expected for hyperthermia activation of the NPs to trigger cellular death. Finally, some tests were performed to further derivatize the immobilized NPs onto surfaces through either a covalent bond or electrostatic interactions. Future work will be dedicated to the recovery of such Janus NPs from the substrate surface.

Neural Correlates of Sensory Substitution in Vestibular Pathways Following Complete Vestibular Loss

PubMed Central

Sadeghi, Soroush G.; Minor, Lloyd B.; Cullen, Kathleen E.

2012-01-01

Sensory substitution is the term typically used in reference to sensory prosthetic devices designed to replace input from one defective modality with input from another modality. Such devices allow an alternative encoding of sensory information that is no longer directly provided by the defective modality in a purposeful and goal-directed manner. The behavioral recovery that follows complete vestibular loss is impressive and has long been thought to take advantage of a natural form of sensory substitution in which head motion information is no longer provided by vestibular inputs, but instead by extra-vestibular inputs such as proprioceptive and motor efference copy signals. Here we examined the neuronal correlates of this behavioral recovery after complete vestibular loss in alert behaving monkeys (Macaca mulata). We show for the first time that extra-vestibular inputs substitute for the vestibular inputs to stabilize gaze at the level of single neurons in the VOR premotor circuitry. The summed weighting of neck proprioceptive and efference copy information was sufficient to explain simultaneously observed behavioral improvements in gaze stability. Furthermore, by altering correspondence between intended and actual head movement we revealed a four-fold increase in the weight of neck motor efference copy signals consistent with the enhanced behavioral recovery observed when head movements are voluntary versus unexpected. Thus, taken together our results provide direct evidence that the substitution by extra-vestibular inputs in vestibular pathways provides a neural correlate for the improvements in gaze stability that are observed following the total loss of vestibular inputs. PMID:23077054

Biocomposite Plasma-Sprayed Coatings Based on Zinc-Substituted Hydroxyapatite: Structure, Properties, and Prospects of Application

NASA Astrophysics Data System (ADS)

Lyasnikova, A. V.; Markelova, O. A.; Lyasnikov, V. N.; Dudareva, O. A.

2016-01-01

The method of synthesis of a zinc-substituted hydroxyapatite powder is presented, and the technology of creating coatings by its spraying is described. The results of studies on the morphological, physical, and chemical parameters of a zinc-substituted hydroxyapatite coating by using X-ray analysis, infrared spectroscopy, transmission electron microscopy, optical microscopy, SEM, and other methods are given.

Preparation and characterization of cobalt-substituted anthrax lethal factor

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

Saebel, Crystal E.; Carbone, Ryan; Dabous, John R.

2011-12-09

Highlights: Black-Right-Pointing-Pointer Cobalt-substituted anthrax lethal factor (CoLF) is highly active. Black-Right-Pointing-Pointer CoLF can be prepared by bio-assimilation and direct exchange. Black-Right-Pointing-Pointer Lethal factor binds cobalt tightly. Black-Right-Pointing-Pointer The electronic spectrum of CoLF reveals penta-coordination. Black-Right-Pointing-Pointer Interaction of CoLF with thioglycolic acid follows a 2-step mechanism. -- Abstract: Anthrax lethal factor (LF) is a zinc-dependent endopeptidase involved in the cleavage of mitogen-activated protein kinase kinases near their N-termini. The current report concerns the preparation of cobalt-substituted LF (CoLF) and its characterization by electronic spectroscopy. Two strategies to produce CoLF were explored, including (i) a bio-assimilation approach involving the cultivation of LF-expressingmore » Bacillus megaterium cells in the presence of CoCl{sub 2}, and (ii) direct exchange by treatment of zinc-LF with CoCl{sub 2}. Independent of the method employed, the protein was found to contain one Co{sup 2+} per LF molecule, and was shown to be twice as active as its native zinc counterpart. The electronic spectrum of CoLF suggests the Co{sup 2+} ion to be five-coordinate, an observation similar to that reported for other Co{sup 2+}-substituted gluzincins, but distinct from that documented for the crystal structure of native LF. Furthermore, spectroscopic studies following the exposure of CoLF to thioglycolic acid (TGA) revealed a sequential mechanism of metal removal from LF, which likely involves the formation of an enzyme: Co{sup 2+}:TGA ternary complex prior to demetallation of the active site. CoLF reported herein constitutes the first spectroscopic probe of LF's active site, which may be utilized in future studies to gain further insight into the enzyme's mechanism and inhibitor interactions.« less

Researcher’s Perspective of Substitution Method on Text Steganography

NASA Astrophysics Data System (ADS)

Zamir Mansor, Fawwaz; Mustapha, Aida; Azah Samsudin, Noor

2017-08-01

The linguistic steganography studies are still in the stage of development and empowerment practices. This paper will present several text steganography on substitution methods based on the researcher’s perspective, all scholar paper will analyse and compared. The objective of this paper is to give basic information in the substitution method of text domain steganography that has been applied by previous researchers. The typical ways of this method also will be identified in this paper to reveal the most effective method in text domain steganography. Finally, the advantage of the characteristic and drawback on these techniques in generally also presented in this paper.

Spacecraft methods and structures with enhanced attitude control that facilitates gyroscope substitutions

NASA Technical Reports Server (NTRS)

Li, Rongsheng (Inventor); Kurland, Jeffrey A. (Inventor); Dawson, Alec M. (Inventor); Wu, Yeong-Wei A. (Inventor); Uetrecht, David S. (Inventor)

2004-01-01

Methods and structures are provided that enhance attitude control during gyroscope substitutions by insuring that a spacecraft's attitude control system does not drive its absolute-attitude sensors out of their capture ranges. In a method embodiment, an operational process-noise covariance Q of a Kalman filter is temporarily replaced with a substantially greater interim process-noise covariance Q. This replacement increases the weight given to the most recent attitude measurements and hastens the reduction of attitude errors and gyroscope bias errors. The error effect of the substituted gyroscopes is reduced and the absolute-attitude sensors are not driven out of their capture range. In another method embodiment, this replacement is preceded by the temporary replacement of an operational measurement-noise variance R with a substantially larger interim measurement-noise variance R to reduce transients during the gyroscope substitutions.

First-principles study on silicon atom doped monolayer graphene

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hussain, Nayyar

2018-01-01

This paper illustrates the structural, electronic and optical properties of individual silicon (Si) atom-doped single layer graphene using density functional theory method. Si atom forms tight bonding with graphene layer. The effect of doping has been investigated by varying the concentration of Si atoms from 3.125% to 9.37% (i.e. From one to three Si atoms in 4 × 4 pure graphene supercell containing 32 carbon atoms), respectively. Electronic structure, partial density of states (PDOS) and optical properties of pure and Si atom-doped graphene sheet were calculated using VASP (Vienna ab-initio Simulation Package). The calculated results for pure graphene sheet were then compared with Si atom doped graphene. It is revealed that upon Si doping in graphene, a finite band gap appears at the high symmetric K-point, thereby making graphene a direct band gap semiconductor. Moreover, the band gap value is directly proportional to the concentration of impurity Si atoms present in graphene lattice. Upon analyzing the optical properties of Si atom-doped graphene structures, it is found that, there is significant change in the refractive index of the graphene after Si atom substitution in graphene. In addition, the overall absorption spectrum of graphene is decreased after Si atom doping. Although a significant red shift in absorption is found to occur towards visible range of radiation when Si atom is substituted in its lattice. The reflectivity of graphene improves in low energy region after Si atom substitution in graphene. These results can be useful for tuning the electronic structure and to manipulate the optical properties of graphene layer in the visible region.

76 FR 39474 - Monthly Median Cost of Funds Reporting, and Publication of Cost of Funds Indices

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-06

... commenter noted that there are ``numerous adjustable interest rate home loans including loans sold to the... original indices; and (B) the substitution of the new indices will result in an interest rate substantially... direct substitute because of recent changes in interest rate relationships resulting from monetary policy...

Principal component analysis of binding energies for single-point mutants of hT2R16 bound to an agonist correlate with experimental mutant cell response.

PubMed

Chen, Derek E; Willick, Darryl L; Ruckel, Joseph B; Floriano, Wely B

2015-01-01

Directed evolution is a technique that enables the identification of mutants of a particular protein that carry a desired property by successive rounds of random mutagenesis, screening, and selection. This technique has many applications, including the development of G protein-coupled receptor-based biosensors and designer drugs for personalized medicine. Although effective, directed evolution is not without challenges and can greatly benefit from the development of computational techniques to predict the functional outcome of single-point amino acid substitutions. In this article, we describe a molecular dynamics-based approach to predict the effects of single amino acid substitutions on agonist binding (salicin) to a human bitter taste receptor (hT2R16). An experimentally determined functional map of single-point amino acid substitutions was used to validate the whole-protein molecular dynamics-based predictive functions. Molecular docking was used to construct a wild-type agonist-receptor complex, providing a starting structure for single-point substitution simulations. The effects of each single amino acid substitution in the functional response of the receptor to its agonist were estimated using three binding energy schemes with increasing inclusion of solvation effects. We show that molecular docking combined with molecular mechanics simulations of single-point mutants of the agonist-receptor complex accurately predicts the functional outcome of single amino acid substitutions in a human bitter taste receptor.

Doping process of p-type GaN nanowires: A first principle study

NASA Astrophysics Data System (ADS)

Xia, Sihao; Liu, Lei; Diao, Yu; Feng, Shu

2017-10-01

The process of p-type doping for GaN nanowires is investigated using calculations starting from first principles. The influence of different doping elements, sites, types, and concentrations is discussed. Results suggest that Mg is an optimal dopant when compared to Be and Zn due to its stronger stability, whereas Be atoms are more inclined to exist in the interspace of a nanowire. Interstitially-doped GaN nanowires show notable n-type conductivity, and thus, Be is not a suitable dopant, which is to be expected since systems with inner substitutional dopants are more favorable than those with surface substitutions. Both interstitial and substitutional doping affect the atomic structure near dopants and induce charge transfer between the dopants and adjacent atoms. By altering doping sites and concentrations, nanowire atomic structures remain nearly constant. Substitutional doping models show p-type conductivity, and Mg-doped nanowires with doping concentrations of 4% showing the strongest p-type conductivity. All doping configurations are direct bandgap semiconductors. This study is expected to direct the preparation of high-quality GaN nanowires.

Polybenzimidazole compounds, polymeric media, and methods of post-polymerization modifications

DOEpatents

Klaehn, John R [Idaho Falls, ID; Peterson, Eric S [Idaho Falls, ID; Wertsching, Alan K [Idaho Falls, ID; Orme, Christopher J [Shelley, ID; Luther, Thomas A [Idaho Falls, ID; Jones, Michael G [Pocatello, ID

2007-08-21

A PBI compound includes imidazole nitrogens at least a portion of which are substituted with an organic-inorganic hybrid moiety. At least 85% of the imidazole nitrogens may be substituted. The organic-inorganic hybrid moiety may be an organosilane moiety, for example, (R)Me.sub.2SiCH.sub.2-- where R is selected from among methyl, phenyl, vinyl, and allyl. The PBI compound may exhibit similar thermal properties in comparison to the unsubstituted PBI. The PBI compound may exhibit a solubility in an organic solvent greater than the solubility of the unsubstituted PBI. The PBI compound may be included in separatory media. A substituted PBI synthesis method may include providing a parent PBI in a less than 5 wt % solvent solution. Substituting may occur at about room temperature and/or at about atmospheric pressure. Substituting may use at least 5 equivalents in relation to the imidazole nitrogens to be substituted or, preferably, about 15.

A Group Action Method for Construction of Strong Substitution Box

NASA Astrophysics Data System (ADS)

Jamal, Sajjad Shaukat; Shah, Tariq; Attaullah, Atta

2017-06-01

In this paper, the method to develop cryptographically strong substitution box is presented which can be used in multimedia security and data hiding techniques. The algorithm of construction depends on the action of a projective general linear group over the set of units of the finite commutative ring. The strength of substitution box and ability to create confusion is assessed with different available analyses. Moreover, the ability of resistance against malicious attacks is also evaluated. The substitution box is examined by bit independent criterion, strict avalanche criterion, nonlinearity test, linear approximation probability test and differential approximation probability test. This substitution box is equated with well-recognized substitution boxes such as AES, Gray, APA, S8, prime of residue, Xyi and Skipjack. The comparison shows encouraging results about the strength of the proposed box. The majority logic criterion is also calculated to analyze the strength and its practical implementation.

Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

DOE R&D Accomplishments Database

Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

1982-04-01

From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

Kinugasa reactions in water: from green chemistry to bioorthogonal labelling.

PubMed

Chigrinova, Mariya; MacKenzie, Douglas A; Sherratt, Allison R; Cheung, Lawrence L W; Pezacki, John Paul; Pezacki, Paul

2015-04-16

The Kinugasa reaction has become an efficient method for the direct synthesis of β-lactams from substituted nitrones and copper(I) acetylides. In recent years, the reaction scope has been expanded to include the use of water as the solvent, and with micelle-promoted [3+2] cycloadditions followed by rearrangement furnishing high yields of β-lactams. The high yields of stable products under aqueous conditions render the modified Kinugasa reaction amenable to metabolic labelling and bioorthogonal applications. Herein, the development of methods for use of the Kinugasa reaction in aqueous media is reviewed, with emphasis on its potential use as a bioorthogonal coupling strategy.

Rare, evolutionarily unlikely missense substitutions in CHEK2 contribute to breast cancer susceptibility: results from a breast cancer family registry case-control mutation-screening study.

PubMed

Le Calvez-Kelm, Florence; Lesueur, Fabienne; Damiola, Francesca; Vallée, Maxime; Voegele, Catherine; Babikyan, Davit; Durand, Geoffroy; Forey, Nathalie; McKay-Chopin, Sandrine; Robinot, Nivonirina; Nguyen-Dumont, Tù; Thomas, Alun; Byrnes, Graham B; Hopper, John L; Southey, Melissa C; Andrulis, Irene L; John, Esther M; Tavtigian, Sean V

2011-01-18

Both protein-truncating variants and some missense substitutions in CHEK2 confer increased risk of breast cancer. However, no large-scale study has used full open reading frame mutation screening to assess the contribution of rare missense substitutions in CHEK2 to breast cancer risk. This absence has been due in part to a lack of validated statistical methods for summarizing risk attributable to large numbers of individually rare missense substitutions. Previously, we adapted an in silico assessment of missense substitutions used for analysis of unclassified missense substitutions in BRCA1 and BRCA2 to the problem of assessing candidate genes using rare missense substitution data observed in case-control mutation-screening studies. The method involves stratifying rare missense substitutions observed in cases and/or controls into a series of grades ordered a priori from least to most likely to be evolutionarily deleterious, followed by a logistic regression test for trends to compare the frequency distributions of the graded missense substitutions in cases versus controls. Here we used this approach to analyze CHEK2 mutation-screening data from a population-based series of 1,303 female breast cancer patients and 1,109 unaffected female controls. We found evidence of risk associated with rare, evolutionarily unlikely CHEK2 missense substitutions. Additional findings were that (1) the risk estimate for the most severe grade of CHEK2 missense substitutions (denoted C65) is approximately equivalent to that of CHEK2 protein-truncating variants; (2) the population attributable fraction and the familial relative risk explained by the pool of rare missense substitutions were similar to those explained by the pool of protein-truncating variants; and (3) post hoc power calculations implied that scaling up case-control mutation screening to examine entire biochemical pathways would require roughly 2,000 cases and controls to achieve acceptable statistical power. This study shows that CHEK2 harbors many rare sequence variants that confer increased risk of breast cancer and that a substantial proportion of these are missense substitutions. The study validates our analytic approach to rare missense substitutions and provides a method to combine data from protein-truncating variants and rare missense substitutions into a one degree of freedom per gene test.

Electron spin resonance (ESR) of magnetic sublattices in Sc-substituted barium hexaferrite

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

Díaz-Pardo, Rebeca; Monjaras, Raúl Valenzuela; Bierlich, Silvia

2016-05-15

The partial substitution of Fe{sup 3+} by Sc{sup 3+} in barium hexaferrite has shown to be an effective method to tailor anisotropy for many novel microwave applications. Some basic studies have revealed that this substitution leads to unusual interactions among the magnetic sublattices of the ferrite. In order to investigate these interactions, samples with formula BaSc{sub x}Fe{sub 12-x}O{sub 19} (1 ≤x ≤ 2) were prepared by sintering (1300°C, 6h). After structural characterization by x-ray diffraction, their ferromagnetic resonance spectra were measured in the X-band (9.4 GHz), in the 100-500 K temperature range. For x = 2, a single, broad resonancemore » peak was observed at the low temperatures (103 K), exhibiting a progressive splitting into two peaks for increasing T, to finally coalesce again into a single (paramagnetic) narrow peak at 473 K. These results are interpreted in terms of a substitution of Fe{sup 3+} by Sc{sup 3+} ions in the 4f{sub vi} and 2b sublattices; the diamagnetic cations disrupt the superexchange interactions and produce a splitting of the 12k sublattice (which interacts directly with the 4f{sub vi} sublattice) into two sublattices with different canting angles, and different thermal dependence. As a result, the fraction of the 12k sublattices that are nearest neighbours of substituted 4f{sub vi} sites can behave as an independent sublattice for some temperature ranges. A similar behavior is observed for all the compositions with varying degrees of amplitude, but it is more evident for x = 2. A deconvolution of peaks has been attempted, in order to shed more light into this behavior.« less

Crystal imperfection studies of pure and silicon substituted hydroxyapatite using Raman and XRD.

PubMed

Zou, Shuo; Huang, Jie; Best, Serena; Bonfield, William

2005-12-01

Hydroxyapatite (HA) is important in biomedical applications because of its chemical similarity to the mineral content of bone and its consequent bioactivity. Silicon substitution into the hydroxyapatite crystal lattice was found to enhance its bioactivity both in vitro and in vivo [1, 2]. However, the mechanism for the enhancement is still not well understood. In this paper, the crystal imperfections introduced by silicon substitution were studied using XRD and Raman spectroscopy. It was found that silicon substitution did not introduce microstrain, but deceased the crystal size in the hk0 direction. Three new vibration modes and peak broadening were observed in Raman spectra following silicon incorporation. The imperfections introduced by silicon substitution may play a role in enhancing bioactivity. A phenomenological relationship between the width of the PO4 v1 peak and crystal size was established.

Optoelectronic Properties of X-Doped (X = O, S, Te) Photovoltaic CSe with Puckered Structure.

PubMed

Zhang, Qiang; Xin, Tianyuan; Lu, Xiaoke; Wang, Yuexia

2018-03-16

We exploited novel two-dimensional (2D) carbon selenide (CSe) with a structure analogous to phosphorene, and probed its electronics and optoelectronics. Calculating phonon spectra using the density functional perturbation theory (DFPT) method indicated that 2D CSe possesses dynamic stability, which made it possible to tune and equip CSe with outstanding properties by way of X-doping (X = O, S, Te), i.e., X substituting Se atoms. Then systematic investigation on the structural, electronic, and optical properties of pristine and X-doped monolayer CSe was carried out using the density functional theory (DFT) method. It was found that the bonding feature of C-X is intimately associated with the electronegativity and radius of the doping atoms, which leads to diverse electronic and optical properties for doping different group VI elements. All the systems possess direct gaps, except for O-doping. Substituting O for Se atoms in monolayer CSe brings about a transition from a direct Γ-Γ band gap to an indirect Γ-Y band gap. Moreover, the value of the band gap decreases with increased doping concentration and radius of doping atoms. A red shift in absorption spectra occurs toward the visible range of radiation after doping, and the red-shift phenomenon becomes more obvious with increased radius and concentration of doping atoms. The results can be useful for filtering doping atoms according to their radius or electronegativity in order to tailor optical spectra efficiently.

Optoelectronic Properties of X-Doped (X = O, S, Te) Photovoltaic CSe with Puckered Structure

PubMed Central

Zhang, Qiang; Xin, Tianyuan; Lu, Xiaoke; Wang, Yuexia

2018-01-01

We exploited novel two-dimensional (2D) carbon selenide (CSe) with a structure analogous to phosphorene, and probed its electronics and optoelectronics. Calculating phonon spectra using the density functional perturbation theory (DFPT) method indicated that 2D CSe possesses dynamic stability, which made it possible to tune and equip CSe with outstanding properties by way of X-doping (X = O, S, Te), i.e., X substituting Se atoms. Then systematic investigation on the structural, electronic, and optical properties of pristine and X-doped monolayer CSe was carried out using the density functional theory (DFT) method. It was found that the bonding feature of C-X is intimately associated with the electronegativity and radius of the doping atoms, which leads to diverse electronic and optical properties for doping different group VI elements. All the systems possess direct gaps, except for O-doping. Substituting O for Se atoms in monolayer CSe brings about a transition from a direct Γ-Γ band gap to an indirect Γ-Y band gap. Moreover, the value of the band gap decreases with increased doping concentration and radius of doping atoms. A red shift in absorption spectra occurs toward the visible range of radiation after doping, and the red-shift phenomenon becomes more obvious with increased radius and concentration of doping atoms. The results can be useful for filtering doping atoms according to their radius or electronegativity in order to tailor optical spectra efficiently. PMID:29547504

Directly auto-transplanted mesenchymal stem cells induce bone formation in a ceramic bone substitute in an ectopic sheep model

PubMed Central

Boos, Anja M; Loew, Johanna S; Deschler, Gloria; Arkudas, Andreas; Bleiziffer, Oliver; Gulle, Heinz; Dragu, Adrian; Kneser, Ulrich; Horch, Raymund E; Beier, Justus P

2011-01-01

Abstract Bone tissue engineering approaches increasingly focus on the use of mesenchymal stem cells (MSC). In most animal transplantation models MSC are isolated and expanded before auto cell transplantation which might be critical for clinical application in the future. Hence this study compares the potential of directly auto-transplanted versus in vitro expanded MSC with or without bone morphogenetic protein-2 (BMP-2) to induce bone formation in a large volume ceramic bone substitute in the sheep model. MSC were isolated from bone marrow aspirates and directly auto-transplanted or expanded in vitro and characterized using fluorescence activated cell sorting (FACS) and RT-PCR analysis before subcutaneous implantation in combination with BMP-2 and β-tricalcium phosphate/hydroxyapatite (β-TCP/HA) granules. Constructs were explanted after 1 to 12 weeks followed by histological and RT-PCR evaluation. Sheep MSC were CD29+, CD44+ and CD166+ after selection by Ficoll gradient centrifugation, while directly auto-transplanted MSC-populations expressed CD29 and CD166 at lower levels. Both, directly auto-transplanted and expanded MSC, were constantly proliferating and had a decreasing apoptosis over time in vivo. Directly auto-transplanted MSC led to de novo bone formation in a heterotopic sheep model using a β-TCP/HA matrix comparable to the application of 60 μg/ml BMP-2 only or implantation of expanded MSC. Bone matrix proteins were up-regulated in constructs following direct auto-transplantation and in expanded MSC as well as in BMP-2 constructs. Up-regulation was detected using immunohistology methods and RT-PCR. Dense vascularization was demonstrated by CD31 immunohistology staining in all three groups. Ectopic bone could be generated using directly auto-transplanted or expanded MSC with β-TCP/HA granules alone. Hence BMP-2 stimulation might become dispensable in the future, thus providing an attractive, clinically feasible approach to bone tissue engineering. PMID:20636333

A Nonstationary Markov Model Detects Directional Evolution in Hymenopteran Morphology.

PubMed

Klopfstein, Seraina; Vilhelmsen, Lars; Ronquist, Fredrik

2015-11-01

Directional evolution has played an important role in shaping the morphological, ecological, and molecular diversity of life. However, standard substitution models assume stationarity of the evolutionary process over the time scale examined, thus impeding the study of directionality. Here we explore a simple, nonstationary model of evolution for discrete data, which assumes that the state frequencies at the root differ from the equilibrium frequencies of the homogeneous evolutionary process along the rest of the tree (i.e., the process is nonstationary, nonreversible, but homogeneous). Within this framework, we develop a Bayesian approach for testing directional versus stationary evolution using a reversible-jump algorithm. Simulations show that when only data from extant taxa are available, the success in inferring directionality is strongly dependent on the evolutionary rate, the shape of the tree, the relative branch lengths, and the number of taxa. Given suitable evolutionary rates (0.1-0.5 expected substitutions between root and tips), accounting for directionality improves tree inference and often allows correct rooting of the tree without the use of an outgroup. As an empirical test, we apply our method to study directional evolution in hymenopteran morphology. We focus on three character systems: wing veins, muscles, and sclerites. We find strong support for a trend toward loss of wing veins and muscles, while stationarity cannot be ruled out for sclerites. Adding fossil and time information in a total-evidence dating approach, we show that accounting for directionality results in more precise estimates not only of the ancestral state at the root of the tree, but also of the divergence times. Our model relaxes the assumption of stationarity and reversibility by adding a minimum of additional parameters, and is thus well suited to studying the nature of the evolutionary process in data sets of limited size, such as morphology and ecology. © The Author(s) 2015. Published by Oxford University Press, on behalf of the Society of Systematic Biologists.

[THE CONDITION AND TENDENCIES OF DEVELOPMENT OF CLINICAL AND SANITARY MICROBIOLOGY IN THE RUSSIAN FEDERATION AND PROBLEM OF IMPORT SUBSTITUTION].

PubMed

Dyatlov, I A; Mironov, A Yu; Shepelin, A P; Aleshkin, V A

2015-08-01

The import substitution becomes one of the strategic tasks of national economy as a result of prolongation of economic sanctions concerning the Russian Federation of part of the USA, EU countries, Japan and number of other countries. It is not proper to be limited in import substitution only by goods because in conditions ofsanctions when access toforeign technologies is complicated Russia is needed to substitute foreign technologies by national designs in faster manner One of directions of effective import substitution is localization of production of laboratory equipment and consumables for clinical and sanitary microbiology on the territory ofthe Russian Federation and countries of Customs union. In Russia, in the field ofdiagnostic of dangerous and socially significant infections, all components for import substitution to implement gene diagnostic, immune diagnostic. bio-sensory and biochip approaches, isolation and storage of live microbial cultures, implementation of high-tech methods of diagnostic are available. At the same time, national diagnostic instrument-making industry for microbiology is factually absent. The few devices of national production more than on 50% consist of import components. The microbiological laboratories are to be equipped only with import devices of open type for applying national components. The most perspective national designs to be implemented are multiplex polimerase chain reaction test-systems and biochips on the basis of national plotters and readers. The modern development of diagnostic equipment and diagnostic instruments requires supplement of national collections of bacterial and viral pathogens and working-through of organizational schemes of supplying collections with strains. The presented data concerning justification of nomenclature of laboratory equipment and consumables permits to satisfy in fill scope the needs of clinical and sanitary microbiology in devices, growth mediums, consumables of national production and to refuse import deliveries without decreasing quality of microbiological analysis. This approach will ensure appropriate response to occurring challenges and new biological dangers and maintenance of biosecurity of the Russian Federation at proper level.

The influence of targeted education on medication persistence and generic substitution among consumer-directed health care enrollees.

PubMed

Sedjo, Rebecca L; Cox, Emily R

2009-12-01

To evaluate an educational outreach among consumer-directed health plan (CDHP) enrollees on medication persistence and lower-cost generic substitution within four chronic medication therapies. A cross-sectional analysis using pharmacy claims data from a national employer group that began offering a CDHP in 2006 and implemented an educational outreach to some CDHP enrollees in 2007 was used. The intervention group was comprised of CDHP enrollees who received education outreach and was compared with CDHP enrollees without the educational outreach. Adjusted and unadjusted medication persistence and lower-cost generic substitutions were compared between groups. There was no difference in medication persistence between groups. CDHP enrollees with the educational outreach were more likely to have converted to lower-cost generic alternative antihypertensive medication compared with CDHP enrollees without the educational outreach (OR(adj)=29.82, 95 percent CI=4.41-201.93). Educational outreach directed to CDHP enrollees was associated with increases in lower-cost generic alternatives with no change in patients' chronic medication use. However, considerable opportunity exists to assist CDHP enrollees in making sound health care decisions.

Tuning the hybridization and magnetic ground state of electron and hole doped CeOs2Al10 : An x-ray spectroscopy study

NASA Astrophysics Data System (ADS)

Chen, Kai; Sundermann, Martin; Strigari, Fabio; Kawabata, Jo; Takabatake, Toshiro; Tanaka, Arata; Bencok, Peter; Choueikani, Fadi; Severing, Andrea

2018-04-01

Here we present linear and circular polarized soft x-ray absorption spectroscopy (XAS) data at the Ce M4 ,5 edges of the electron (Ir) and hole-doped (Re) Kondo semiconductor CeOs2Al10 . Both substitutions have a strong impact on the unusual high Néel temperature TN=28.5 K, and also the direction of the ordered moment in case of Ir. The substitution dependence of the linear dichroism is weak thus validating the crystal-field description of CeOs2Al10 being representative for the Re and Ir substituted compounds. The impact of electron and hole doping on the hybridization between conduction and 4 f electrons is related to the amount of f0 in the ground state and reduction of x-ray magnetic circular dichroism. A relationship of c f -hybridization strength and enhanced TN is discussed. The direction and doping dependence of the circular dichroism strongly supports the idea of strong Kondo screening along the crystallographic a direction.

On Medical Progress and Health Care Demand: A Ces Perspective Using the Grossman Model of Health Status.

PubMed

Batinti, Alberto

2015-12-01

I propose an application of the pure-consumption version of the Grossman model of health care demand, where utility depends on consumption and health status and health status on medical care and health technology. I derive the conditions under which an improvement in health care technology leads to an increase/decrease in health care consumption. In particular, I show how the direction of the effect depends on the relationship between the constant elasticity of substitution parameters of the utility and health production functions. I find that, under the constancy assumption, the ratio of the two elasticity of substitution parameters determines the direction of a technological change on health care demand. On the other hand, the technology share parameter in the health production function contributes to the size but not to the direction of the technological effect. I finally explore how the ratio of the elasticity of substitution parameters work in measurement and practice and discuss how future research may use the theoretical insight provided here. Copyright © 2014 John Wiley & Sons, Ltd.

Effect of multinary substitution on electronic and transport properties of TiCoSb based half-Heusler alloys

NASA Astrophysics Data System (ADS)

Choudhary, Mukesh K.; Ravindran, P.

2018-05-01

The electronic structures of TixZrx/2CoPbxTex, TixZrx/2Hfx/2CoPbxTex (x = 0.5), and the parent compound TiCoSb were investigated using the full potential linearized augmented plane wave method. The thermoelectric transport properties of these alloys are calculated on the basis of semi-classical Boltzmann transport theory. From the band structure calculations we show that the substitution of Zr,Hf in the Ti site and Pb and Te in the Sb site lower the band gap value and also change the indirect band (IB) gap of TiCoSb to the direct band (DB) gap. The calculated band gap of TiCoSb, TixZrx/2CoPbxTex, and TixZrx/2Hfx/2CoPbxTex are 1.04 eV (IB), 0.92 eV (DB), and 0.93 eV (DB), respectively. All these alloys follow the empirical rule of 18 valence-electron content which is essential for bringing semiconductivity in half Heusler alloys. It is shown that the substitution of Hf at the Ti site improve the ZT value (˜1.05) at room temperature, whereas there is no significant difference in ZT is found at higher temperature. Based on the calculated thermoelectric transport properties, we conclude that the appropriate concentration of Hf substitution can further improve the thermoelectric performance of TixZrx/2Hfx/2CoPbxTex.

Modeling HIV-1 Drug Resistance as Episodic Directional Selection

PubMed Central

Murrell, Ben; de Oliveira, Tulio; Seebregts, Chris; Kosakovsky Pond, Sergei L.; Scheffler, Konrad

2012-01-01

The evolution of substitutions conferring drug resistance to HIV-1 is both episodic, occurring when patients are on antiretroviral therapy, and strongly directional, with site-specific resistant residues increasing in frequency over time. While methods exist to detect episodic diversifying selection and continuous directional selection, no evolutionary model combining these two properties has been proposed. We present two models of episodic directional selection (MEDS and EDEPS) which allow the a priori specification of lineages expected to have undergone directional selection. The models infer the sites and target residues that were likely subject to directional selection, using either codon or protein sequences. Compared to its null model of episodic diversifying selection, MEDS provides a superior fit to most sites known to be involved in drug resistance, and neither one test for episodic diversifying selection nor another for constant directional selection are able to detect as many true positives as MEDS and EDEPS while maintaining acceptable levels of false positives. This suggests that episodic directional selection is a better description of the process driving the evolution of drug resistance. PMID:22589711

Modeling HIV-1 drug resistance as episodic directional selection.

PubMed

Murrell, Ben; de Oliveira, Tulio; Seebregts, Chris; Kosakovsky Pond, Sergei L; Scheffler, Konrad

2012-01-01

The evolution of substitutions conferring drug resistance to HIV-1 is both episodic, occurring when patients are on antiretroviral therapy, and strongly directional, with site-specific resistant residues increasing in frequency over time. While methods exist to detect episodic diversifying selection and continuous directional selection, no evolutionary model combining these two properties has been proposed. We present two models of episodic directional selection (MEDS and EDEPS) which allow the a priori specification of lineages expected to have undergone directional selection. The models infer the sites and target residues that were likely subject to directional selection, using either codon or protein sequences. Compared to its null model of episodic diversifying selection, MEDS provides a superior fit to most sites known to be involved in drug resistance, and neither one test for episodic diversifying selection nor another for constant directional selection are able to detect as many true positives as MEDS and EDEPS while maintaining acceptable levels of false positives. This suggests that episodic directional selection is a better description of the process driving the evolution of drug resistance.

Comparison of different methods to include recycling in LCAs of aluminium cans and disposable polystyrene cups.

PubMed

van der Harst, Eugenie; Potting, José; Kroeze, Carolien

2016-02-01

Many methods have been reported and used to include recycling in life cycle assessments (LCAs). This paper evaluates six widely used methods: three substitution methods (i.e. substitution based on equal quality, a correction factor, and alternative material), allocation based on the number of recycling loops, the recycled-content method, and the equal-share method. These six methods were first compared, with an assumed hypothetical 100% recycling rate, for an aluminium can and a disposable polystyrene (PS) cup. The substitution and recycled-content method were next applied with actual rates for recycling, incineration and landfilling for both product systems in selected countries. The six methods differ in their approaches to credit recycling. The three substitution methods stimulate the recyclability of the product and assign credits for the obtained recycled material. The choice to either apply a correction factor, or to account for alternative substituted material has a considerable influence on the LCA results, and is debatable. Nevertheless, we prefer incorporating quality reduction of the recycled material by either a correction factor or an alternative substituted material over simply ignoring quality loss. The allocation-on-number-of-recycling-loops method focusses on the life expectancy of material itself, rather than on a specific separate product. The recycled-content method stimulates the use of recycled material, i.e. credits the use of recycled material in products and ignores the recyclability of the products. The equal-share method is a compromise between the substitution methods and the recycled-content method. The results for the aluminium can follow the underlying philosophies of the methods. The results for the PS cup are additionally influenced by the correction factor or credits for the alternative material accounting for the drop in PS quality, the waste treatment management (recycling rate, incineration rate, landfilling rate), and the source of avoided electricity in case of waste incineration. The results for the PS cup, which are less dominated by production of virgin material than aluminium can, furthermore depend on the environmental impact categories. This stresses the importance to consider other impact categories besides the most commonly used global warming impact. The multitude of available methods complicates the choice of an appropriate method for the LCA practitioner. New guidelines keep appearing and industries also suggest their own preferred method. Unambiguous ISO guidelines, particularly related to sensitivity analysis, would be a great step forward in making more robust LCAs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modified nucleotides reveal the indirect role of the central base pairs in stabilizing the lac repressor-operator complex.

PubMed Central

Zhang, X; Gottlieb, P A

1995-01-01

Guanine residues in the lac operator were replaced by 2-aminopurine or purine analogues, pairing the modified nucleotides with C. The observed equilibrium dissociation constants for lac repressor binding to substituted operators were measured in 10 mM Tris, 150 mM KCl, 0.1 mM EDTA, 0.1 mM DTE, pH 7.6 at 25 degrees C. These measurements revealed five positions that destabilized the complex when substituted with either analogue. Two positions, which are related by a 2-fold symmetry, are in the major groove of the operator thought to directly interact with the protein. Three sites were in the central region of the operator. A purine analogue at a sixth site perturbed the local DNA structure and destabilized the complex. Alkylation interference experiments of the 2-aminopurine substituted operators demonstrated that, of the five affected, two substitutions displayed altered phosphate interference patterns at the phosphate adjacent to the substituted base. For these operators, complex formation was measured in different concentrations of KCl to assess the contribution of counterion release to the bimolecular process. The results indicated that both complexes were similar to wild-type, although minor changes were observed. The Kobs of the complex was then measured when 2-aminopurine or purine analogues were paired with uracil nucleotide, a base pair that serves to stabilize the DNA. The introduction of the new base pairs revealed two effects on the bimolecular interaction. For those operator sites that are thought to perturb the interaction directly, the affinity of the complex was weakened to levels observed for the singly-substituted operators. In contrast, the nucleotides of 2-aminopurine paired with uracil positioned in the central region of the operator served to enhance the stability of the complex. The purine-uracil base pair substitution on the other hand had a significant destabilizing effect on the interaction. We propose that the central base pairs modulate binding of the complex by altering the intrinsic properties of the DNA. Two specific attributes are required to achieve the lowest free energy of interaction. The DNA must have two interstrand hydrogen bonds to stabilize the duplex and it must have properties associated with directional bending or unwinding. This analysis does not rule out contributions by direct interactions between the protein and the central region of the operator but underscores how indirect effects play a major role in complex formation in this system. Images PMID:7784203

40 CFR Appendix B to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

Code of Federal Regulations, 2013 CFR

2013-07-01

... inches) and right-hand thread direction for CO2 refrigerant service containers.3 Manufacturers should... Failure Mode and Effect Analysis in Manufacturing and Assembly Process [Process FMEA] on the MVAC as... submitted to demonstrate it can be used safely in this end-use. CFC-11, CFC-12, R-502 Industrial Process...

40 CFR Appendix B to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

Code of Federal Regulations, 2014 CFR

2014-07-01

... inches) and right-hand thread direction for CO2 refrigerant service containers.3 Manufacturers should... Failure Mode and Effect Analysis in Manufacturing and Assembly Process [Process FMEA] on the MVAC as... submitted to demonstrate it can be used safely in this end-use. CFC-11, CFC-12, R-502 Industrial Process...

Sustainable Pathways to Pyrroles through Iron-Catalyzed N-Heterocyclization from Unsaturated Diols and Primary Amines.

PubMed

Yan, Tao; Barta, Katalin

2016-09-08

Pyrroles are prominent scaffolds in pharmaceutically active compounds and play an important role in medicinal chemistry. Therefore, the development of new, atom-economic, and sustainable catalytic strategies to obtain these moieties is highly desired. Direct catalytic pathways that utilize readily available alcohol substrates have been recently established; however, these approaches rely on the use of noble metals such as ruthenium or iridium. Here, we report on the direct synthesis of pyrroles using a catalyst based on the earth-abundant and inexpensive iron. The method uses 2-butyne-1,4-diol or 2-butene-1,4-diol that can be directly coupled with anilines, benzyl amines, and aliphatic amines to obtain a variety of N-substituted pyrroles in moderate-to-excellent isolated yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Where does the electron go? The nature of ortho/para and meta group directing in electrophilic aromatic substitution

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

Liu, Shubin, E-mail: shubin@email.unc.edu

Electrophilic aromatic substitution as one of the most fundamental chemical processes is affected by atoms or groups already attached to the aromatic ring. The groups that promote substitution at the ortho/para or meta positions are, respectively, called ortho/para and meta directing groups, which are often characterized by their capability to donate electrons to or withdraw electrons from the ring. Though resonance and inductive effects have been employed in textbooks to explain this phenomenon, no satisfactory quantitative interpretation is available in the literature. Here, based on the theoretical framework we recently established in density functional reactivity theory (DFRT), where electrophilicity andmore » nucleophilicity are simultaneously quantified by the Hirshfeld charge, the nature of ortho/para and meta group directing is systematically investigated for a total of 85 systems. We find that regioselectivity of electrophilic attacks is determined by the Hirshfeld charge distribution on the aromatic ring. Ortho/para directing groups have most negative charges on the ortho/para positions, while meta directing groups often possess the largest negative charge on the meta position. Our results do not support that ortho/para directing groups are electron donors and meta directing groups are electron acceptors. Most neutral species we studied here are electron withdrawal in nature. Anionic systems are always electron donors. There are also electron donors serving as meta directing groups. We predicted ortho/para and meta group directing behaviors for a list of groups whose regioselectivity is previously unknown. In addition, strong linear correlations between the Hirshfeld charge and the highest occupied molecular orbital have been observed, providing the first link between the frontier molecular orbital theory and DFRT.« less

A Comparison of the β-Substitution Method and a Bayesian Method for Analyzing Left-Censored Data

PubMed Central

Huynh, Tran; Quick, Harrison; Ramachandran, Gurumurthy; Banerjee, Sudipto; Stenzel, Mark; Sandler, Dale P.; Engel, Lawrence S.; Kwok, Richard K.; Blair, Aaron; Stewart, Patricia A.

2016-01-01

Classical statistical methods for analyzing exposure data with values below the detection limits are well described in the occupational hygiene literature, but an evaluation of a Bayesian approach for handling such data is currently lacking. Here, we first describe a Bayesian framework for analyzing censored data. We then present the results of a simulation study conducted to compare the β-substitution method with a Bayesian method for exposure datasets drawn from lognormal distributions and mixed lognormal distributions with varying sample sizes, geometric standard deviations (GSDs), and censoring for single and multiple limits of detection. For each set of factors, estimates for the arithmetic mean (AM), geometric mean, GSD, and the 95th percentile (X0.95) of the exposure distribution were obtained. We evaluated the performance of each method using relative bias, the root mean squared error (rMSE), and coverage (the proportion of the computed 95% uncertainty intervals containing the true value). The Bayesian method using non-informative priors and the β-substitution method were generally comparable in bias and rMSE when estimating the AM and GM. For the GSD and the 95th percentile, the Bayesian method with non-informative priors was more biased and had a higher rMSE than the β-substitution method, but use of more informative priors generally improved the Bayesian method’s performance, making both the bias and the rMSE more comparable to the β-substitution method. An advantage of the Bayesian method is that it provided estimates of uncertainty for these parameters of interest and good coverage, whereas the β-substitution method only provided estimates of uncertainty for the AM, and coverage was not as consistent. Selection of one or the other method depends on the needs of the practitioner, the availability of prior information, and the distribution characteristics of the measurement data. We suggest the use of Bayesian methods if the practitioner has the computational resources and prior information, as the method would generally provide accurate estimates and also provides the distributions of all of the parameters, which could be useful for making decisions in some applications. PMID:26209598

Coestimation of recombination, substitution and molecular adaptation rates by approximate Bayesian computation.

PubMed

Lopes, J S; Arenas, M; Posada, D; Beaumont, M A

2014-03-01

The estimation of parameters in molecular evolution may be biased when some processes are not considered. For example, the estimation of selection at the molecular level using codon-substitution models can have an upward bias when recombination is ignored. Here we address the joint estimation of recombination, molecular adaptation and substitution rates from coding sequences using approximate Bayesian computation (ABC). We describe the implementation of a regression-based strategy for choosing subsets of summary statistics for coding data, and show that this approach can accurately infer recombination allowing for intracodon recombination breakpoints, molecular adaptation and codon substitution rates. We demonstrate that our ABC approach can outperform other analytical methods under a variety of evolutionary scenarios. We also show that although the choice of the codon-substitution model is important, our inferences are robust to a moderate degree of model misspecification. In addition, we demonstrate that our approach can accurately choose the evolutionary model that best fits the data, providing an alternative for when the use of full-likelihood methods is impracticable. Finally, we applied our ABC method to co-estimate recombination, substitution and molecular adaptation rates from 24 published human immunodeficiency virus 1 coding data sets.

Organocatalytic asymmetric arylation of indoles enabled by azo groups

NASA Astrophysics Data System (ADS)

Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin

2018-01-01

Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

Organocatalytic asymmetric arylation of indoles enabled by azo groups.

PubMed

Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin

2018-01-01

Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

Chemical alternatives assessment: the case of flame retardants.

PubMed

Howard, Gregory J

2014-12-01

Decisions on chemical substitution are made rapidly and by many stakeholders; these decisions may have a direct impact on consumer exposures, and, when a hazard exists, to consumer risks. Flame retardants (FRs) represent particular challenges, including very high production volumes, designed-in persistence, and often direct consumer exposure. Newer FR products, as with other industrial chemicals, typically lack data on hazard and exposure, and in many cases even basic information on structure and use in products is unknown. Chemical alternatives assessment (CAA) provides a hazard-focused approach to distinguishing between possible substitutions; variations on this process are used by several government and numerous corporate entities. By grouping chemicals according to functional use, some information on exposure potential can be inferred, allowing for decisions based on those hazard properties that are most distinguishing. This approach can help prevent the "regrettable substitution" of one chemical with another of equal, or even higher, risk. Copyright © 2014 Elsevier Ltd. All rights reserved.

How to Make a Heart Valve: From Embryonic Development to Bioengineering of Living Valve Substitutes

PubMed Central

MacGrogan, Donal; Luxán, Guillermo; Driessen-Mol, Anita; Bouten, Carlijn; Baaijens, Frank; de la Pompa, José Luis

2014-01-01

Cardiac valve disease is a significant cause of ill health and death worldwide, and valve replacement remains one of the most common cardiac interventions in high-income economies. Despite major advances in surgical treatment, long-term therapy remains inadequate because none of the current valve substitutes have the potential for remodeling, regeneration, and growth of native structures. Valve development is coordinated by a complex interplay of signaling pathways and environmental cues that cause disease when perturbed. Cardiac valves develop from endocardial cushions that become populated by valve precursor mesenchyme formed by an epithelial–mesenchymal transition (EMT). The mesenchymal precursors, subsequently, undergo directed growth, characterized by cellular compartmentalization and layering of a structured extracellular matrix (ECM). Knowledge gained from research into the development of cardiac valves is driving exploration into valve biomechanics and tissue engineering directed at creating novel valve substitutes endowed with native form and function. PMID:25368013

Potential savings associated with drug substitution in Medicare Part D: the Translating Research into Action for Diabetes (TRIAD) study.

PubMed

Duru, O Kenrik; Ettner, Susan L; Turk, Norman; Mangione, Carol M; Brown, Arleen F; Fu, Jeffery; Simien, Leslie; Tseng, Chien-Wen

2014-01-01

Drug substitution is a promising approach to reducing medication costs. To calculate the potential savings in a Medicare Part D plan from generic or therapeutic substitution for commonly prescribed drugs. Cross-sectional, simulation analysis. Low-income subsidy (LIS) beneficiaries (n = 145,056) and non low-income subsidy (non-LIS) beneficiaries (n = 1,040,030) enrolled in a large, national Part D health insurer in 2007 and eligible for a possible substitution. Using administrative data from 2007, we identified claims filled for brand-name drugs for which a direct generic substitute was available. We also identified the 50 highest cost drugs separately for LIS and non-LIS beneficiaries, and reached consensus on which drugs had possible therapeutic substitutes (27 for LIS, 30 for non-LIS). For each possible substitution, we used average daily costs of the original and substitute drugs to calculate the potential out-of-pocket savings, health plan savings, and when applicable, savings for the government/LIS subsidy. Overall, 39 % of LIS beneficiaries and 51 % of non-LIS beneficiaries were eligible for a generic and/or therapeutic substitution. Generic substitutions resulted in an average annual savings of $160 in the case of LIS beneficiaries and $127 in the case of non-LIS beneficiaries. Therapeutic substitutions resulted in an average annual savings of $452 in the case of LIS beneficiaries and $389 in the case of non-LIS beneficiaries. Our findings indicate that drug substitution, particularly therapeutic substitution, could result in significant cost savings. There is a need for additional studies evaluating the acceptability of therapeutic substitution interventions within Medicare Part D.

Scanning electron microscopy of high-pressure-frozen sea urchin embryos.

PubMed

Walther, P; Chen, Y; Malecki, M; Zoran, S L; Schatten, G P; Pawley, J B

1993-12-01

High-pressure-freezing permits direct cryo-fixation of sea urchin embryos having a defined developmental state without the formation of large ice crystals. We have investigated preparation protocols for observing high-pressure-frozen and freeze-fractured samples in the scanning electron microscope. High-pressure-freezing was superior to other freezing protocols, because the whole bulk sample was reasonably well frozen and the overall three-dimensional shape of the embryos was well preserved. The samples were either dehydrated by freeze-substitution and critical-point-drying, or imaged in the partially hydrated state, using a cold stage in the SEM. During freeze-substitution the samples were stabilized by fixatives. The disadvantage of this method was that shrinking and extraction effects, caused by the removal of the water, could not be avoided. These disadvantages were avoided when the sample was imaged in the frozen-hydrated state using a cold-stage in the SEM. This would be the method of choice for morphometric studies. Frozen-hydrated samples, however, were very beam sensitive and many structures remained covered by the ice and were not visible. Frozen-hydrated samples were partially freeze-dried to make visible additional structures that had been covered by ice. However, this method also caused drying artifacts when too much water was removed.

Four novel RS1 gene mutations in Polish patients with X-linked juvenile retinoschisis

PubMed Central

Skorczyk, Anna

2012-01-01

Purpose To determine the clinical features and to identify mutations in the retinoschisis gene (RS1) in ten patients with X-linked retinoschisis (XLRS). Methods Ten male patients from nine Polish families were included in this study. Ophthalmologic examinations, including optical coherence tomography (OCT) and full-field electroretinography (ERG), were performed in all affected boys. The entire coding region encompassing six exons of the RS1 gene was amplified with PCR and directly sequenced in all the patients. Results All affected individuals showed typical retinoschisis signs and symptoms, and all appeared to have a mutation in the RS1 gene. Seven different mutations were identified, including two novel missense substitutions: c.176G>C (p.Cys59Ser), c.451T>A (p.Tyr151Asp); one novel nonsense substitution: c.218C>A (p.Ser73*); and one novel frameshift mutation: c.354_355delCA (p.Asp118Glufs*2). We also found two missense substitutions that had been previously described: c.214G>A (p.Glu72Lys) and c.626G>T (p.Arg209Leu) and one known splice site mutation in intron 5: c.522+1G>T (IVS5+1G>T). Conclusions This study provides the first molecular genetic characteristics of patients with juvenile retinoschisis from the previously unexplored Polish population. We investigated the molecular background of XLRS in ten boys. The present study reports for the first time four novel mutations, including two missense substitutions, one nonsense substitution, and one frameshift deletion. One of these substitutions and 2-bp deletion created stop codons. Moreover, we described three substitutions that had been previously reported (one is a splicing mutation). Further genetic characterization of Polish patients with XLRS will be helpful in understanding the worldwide spectrum of RS1 mutations. Despite the mutation heterogeneity found in a small group of our patients, they presented a relatively uniform clinical picture. Identifying the causative mutation is helpful in confirming diagnosis and counseling, but cannot provide prognostic data. PMID:23288992

Iron-catalyzed stereospecific activation of olefinic C-H bonds with Grignard reagent for synthesis of substituted olefins.

PubMed

Ilies, Laurean; Asako, Sobi; Nakamura, Eiichi

2011-05-25

The reaction of an aryl Grignard reagent with a cyclic or acyclic olefin possessing a directing group such as pyridine or imine results in the stereospecific substitution of the olefinic C-H bond syn to the directing group. The reaction takes place smoothly and without isomerization of the product olefin in the presence of a mild oxidant (1,2-dichloro-2-methylpropane) and an aromatic cosolvent. Several lines of evidence suggest that the reaction proceeds via iron-catalyzed olefinic C-H bond activation rather than an oxidative Mizoroki-Heck-type reaction.

Fast synthesis of La-substituted apatite by the dry mechanochemical method and analysis of its structure

NASA Astrophysics Data System (ADS)

Bulina, Natalia V.; Chaikina, Marina V.; Prosanov, Igor Yu.; Dudina, Dina V.; Solovyov, Leonid A.

2017-08-01

Compared to pure apatite, La-substituted apatites have improved thermal, mechanical and biological characteristics. In this article, a fast synthesis of La-substituted apatites by a dry mechanochemical method is presented. Structural studies by X-ray diffraction and Fourier transform infrared spectroscopy indicated the formation of a single-phase nanosized product after 30 min of high-energy ball milling of the reaction mixtures. The dry mechanochemical method is technologically attractive for the preparation of La-substituted apatites, as it allows reducing the processing time down to half an hour and does not require prolonged high-temperature annealing normally used in the synthesis practice of the substituted apatite. As the mechanochemically synthesized samples are nanosized, it is difficult to determine the details of their crystal structure by the Rietveld refinement method. Therefore, a series of the mechanochemically synthesized samples with different concentrations of lanthanum were annealed at 1000°C for 5 h. It was found that the annealed powders are microcrystalline La-substituted apatites Ca10-xLax(PO4)6Ox(OH)2-x, where 0 ≤ x ≤2. In their structure, the Ca2+ ions are replaced by the La3+ ions localized near the Ca2 sites, and the OH- groups are replaced by the O2- ions in the hexagonal channels.

Functional Compensation of a Detrimental Amino Acid Substitution in a Cytotoxic-T-Lymphocyte Epitope of Influenza A Viruses by Comutations

PubMed Central

Rimmelzwaan, G. F.; Berkhoff, E. G. M.; Nieuwkoop, N. J.; Fouchier, R. A. M.; Osterhaus, A. D. M. E.

2004-01-01

Influenza A viruses accumulate amino acid substitutions in cytotoxic-T-lymphocyte (CTL) epitopes, allowing these viruses to escape from CTL immunity. The arginine-to-glycine substitution at position 384 of the viral nucleoprotein is associated with escape from CTLs. Introduction of the R384G substitution in the nucleoprotein gene segment of influenza virus A/Hong Kong/2/68 by site-directed mutagenesis was detrimental to viral fitness. Introduction of one of the comutations associated with R384G, E375G, partially restored viral fitness and nucleoprotein functionality. We hypothesized that influenza A viruses need to overcome functional constraints to accumulate mutations in CTL epitopes and escape from CTLs. PMID:15280506

Parents Accidentally Substitute Similar Sounding Sibling Names More Often than Dissimilar Names

PubMed Central

Griffin, Zenzi M.; Wangerman, Thomas

2013-01-01

When parents select similar sounding names for their children, do they set themselves up for more speech errors in the future? Questionnaire data from 334 respondents suggest that they do. Respondents whose names shared initial or final sounds with a sibling’s reported that their parents accidentally called them by the sibling’s name more often than those without such name overlap. Having a sibling of the same gender, similar appearance, or similar age was also associated with more frequent name substitutions. Almost all other name substitutions by parents involved other family members and over 5% of respondents reported a parent substituting the name of a pet, which suggests a strong role for social and situational cues in retrieving personal names for direct address. To the extent that retrieval cues are shared with other people or animals, other names become available and may substitute for the intended name, particularly when names sound similar. PMID:24391955

Research of Energy Substitution Strategy of China

NASA Astrophysics Data System (ADS)

Zhang, Lifeng; kai, Chen

For a long time, China's energy endowment structure determines the production structure and consumption structure of energy are coal-based.This situation is difficult to change for quite a long time. With the rapid economic growth, industrialization and urbanization, the demand for energy, especially for oil, natural gas will continue to increase. But the oil and gas supply can not meet the needs of rapid growth. The most direct way is to import, and imports will be charged by the international energy situation, and will affect energy and economic security. In view of our country abundant coal resources, we can consider to use coal substituting oil and natural gas to reduce dependence on foreign energy, to strengthen energy and economic security. Therefore, using translog production function, the text forecasts substitution elasticity and the marginal substitution rate between the capital, coal, oil and natural gas, and puts forward substitution program.

[A new contraceptive method: breast feeding].

PubMed

Townsend, S

1993-08-01

Even though women have known for centuries that breast feeding has a contraceptive effect, family planning agents have only recently promoted it. Family planning specialists at a meeting in Bellagio, Italy, on breast feeding developed directives referred to as the Lactational Amenorrhea Method (LAM). Adherence to these directives assure effective protection against pregnancy until resumption of menstruation, expansion of infant feeding to foods other than breast milk, or until 6 months postpartum. Nipple stimulation during suckling is sufficient to suppress ovulation. Frequent suckling or more intense suckling maintains the contraceptive effect, so the directives insist that mothers exclusively or almost exclusively breast feed their infants. LAM provides 98% effective protection against pregnancy for 6 months if women observe it as directed. After 6 months, they should use another family planning method. Scientists are trying to see whether they can make the directives more simple. They will discuss this possibility at their next international meeting in 1993 or 1994. Research indicates that the most crucial rule is amenorrhea and use of this rule will make LAM more easy to learn and use, thereby increasing its use. It is difficult to motivate hospital and family planning clinic staff to promote LAM. Information and education are needed to support LAM. for example, a project in Honduras is using peer counseling to promote LAM. Family Health International is following 1000 women for 1 year postpartum in Pakistan and the Philippines. This study's 6-month LAM efficacy rate was around 95%. Little research has looked at the cost effectiveness of LAM. Optimally, LAM is a temporary contraceptive method which must be followed immediately by another contraceptive method. Indeed, LAM counseling should often pregnancy. LAM supporters do not intend for LAM to be a substitute for family planning, but want LAM to be another method in the contraceptive method mix.

The solitary wave solution of coupled Klein-Gordon-Zakharov equations via two different numerical methods

NASA Astrophysics Data System (ADS)

Dehghan, Mehdi; Nikpour, Ahmad

2013-09-01

In this research, we propose two different methods to solve the coupled Klein-Gordon-Zakharov (KGZ) equations: the Differential Quadrature (DQ) and Globally Radial Basis Functions (GRBFs) methods. In the DQ method, the derivative value of a function with respect to a point is directly approximated by a linear combination of all functional values in the global domain. The principal work in this method is the determination of weight coefficients. We use two ways for obtaining these coefficients: cosine expansion (CDQ) and radial basis functions (RBFs-DQ), the former is a mesh-based method and the latter categorizes in the set of meshless methods. Unlike the DQ method, the GRBF method directly substitutes the expression of the function approximation by RBFs into the partial differential equation. The main problem in the GRBFs method is ill-conditioning of the interpolation matrix. Avoiding this problem, we study the bases introduced in Pazouki and Schaback (2011) [44]. Some examples are presented to compare the accuracy and easy implementation of the proposed methods. In numerical examples, we concentrate on Inverse Multiquadric (IMQ) and second-order Thin Plate Spline (TPS) radial basis functions. The variable shape parameter (exponentially and random) strategies are applied in the IMQ function and the results are compared with the constant shape parameter.

Direct Alkynylation of 3H-Imidazo[4,5-b]pyridines Using gem-Dibromoalkenes as Alkynes Source.

PubMed

Aziz, Jessy; Baladi, Tom; Piguel, Sandrine

2016-05-20

C2 direct alkynylation of 3H-imidazo[4,5-b]pyridine derivatives is explored for the first time. Stable and readily available 1,1-dibromo-1-alkenes, electrophilic alkyne precursors, are used as coupling partners. The simple reaction conditions include an inexpensive copper catalyst (CuBr·SMe2 or Cu(OAc)2), a phosphine ligand (DPEphos) and a base (LiOtBu) in 1,4-dioxane at 120 °C. This C-H alkynylation method revealed to be compatible with a variety of substitutions on both coupling partners: heteroarenes and gem-dibromoalkenes. This protocol allows the straightforward synthesis of various 2-alkynyl-3H-imidazo[4,5-b]pyridines, a valuable scaffold in drug design.

Effect of SiC buffer layer on GaN growth on Si via PA-MBE

NASA Astrophysics Data System (ADS)

Kukushkin, S. A.; Mizerov, A. M.; Osipov, A. V.; Redkov, A. V.; Telyatnik, R. S.; Timoshnev, S. N.

2017-11-01

The study is devoted to comparison of GaN thin films grown on SiC/Si substrates made by the method of atoms substitution with the films grown directly on Si substrates. The growth was performed in a single process via plasma assisted molecular beam epitaxy. The samples were studied via optical microscopy, Raman spectroscopy, ellipsometry, and a comparison of their characteristics was made. Using chemical etching in KOH, the polarity of GaN films grown on SiC/Si and Si substrates was determined.

Human genetics: measuring the raw material of evolution.

PubMed

Armour, John A L

2009-09-15

By direct sequencing of two Y chromosomes inherited from the same paternal ancestor, a landmark study has derived a good direct estimate for the rate of base substitution mutations on the human Y chromosome.

Profiling procedure for disk cutter to generate the male rotor, screw compressors component, using the “Substitute Family Circle” - graphic method in AUTOCAD environment

NASA Astrophysics Data System (ADS)

Popa, CL; Popa, V.

2016-11-01

This paper proposes a profiling method for the tool which generates the helical groove of male rotor, screw compressor component. The method is based on a complementary theorem of surfaces enveloping - "Substitute Family Circles Method”. The specific theorem of family circles of substitution has been applied using AUTOCAD graphics design environment facility. The frontal view of the male rotor, screw compressor component, has been determinate knowing the transverse profile of female rotor, and using this theorem of "Substitute Family Circle". The three-dimensional model of the rotor makes possible to apply the same theorem, leading to the surface of revolution enveloping the helical surface. An application will be also presented to determine the axial profile of the disk cutter, numeric and graphics, following the proposed algorithm.

40 CFR Appendix H to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes, Effective May 28, 1999

Code of Federal Regulations, 2014 CFR

2014-07-01

... inch or the thread direction must be reversed (i.e. right-handed vs. left-handed). Simply changing the thread pitch is not sufficient. For quick-connect fittings, “differ” means that a person using normal... Acceptable subject to narrowed use limits. Acceptable when manufactured using any process that does not...

40 CFR Appendix H to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes, Effective May 28, 1999

Code of Federal Regulations, 2013 CFR

2013-07-01

... inch or the thread direction must be reversed (i.e. right-handed vs. left-handed). Simply changing the thread pitch is not sufficient. For quick-connect fittings, “differ” means that a person using normal... Acceptable subject to narrowed use limits. Acceptable when manufactured using any process that does not...

40 CFR Appendix H to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes, Effective May 28, 1999

Code of Federal Regulations, 2012 CFR

2012-07-01

... inch or the thread direction must be reversed (i.e. right-handed vs. left-handed). Simply changing the thread pitch is not sufficient. For quick-connect fittings, “differ” means that a person using normal... Acceptable subject to narrowed use limits. Acceptable when manufactured using any process that does not...

(E)-3-(4-Chloro­phen­yl)-1-(4-fluoro­phenyl)­prop-2-en-1-one

PubMed Central

Fun, Hoong-Kun; Chia, Tze Shyang; Sapnakumari, M.; Narayana, B.; Sarojini, B. K.

2012-01-01

In the title compound, C15H10ClFO, the fluoro-substituted benzene ring forms a dihedral angle of 44.41 (6)° with the chloro-substituted benzene ring. The only significant directional bonds in the crystal are weak C—H⋯π inter­actions. PMID:22412535

Methods and intermediates for the synthesis of dipyrrin-substituted porphyrinic macrocycles

DOEpatents

Yu, Lianhe; Muthukumaran, Kannan; Sreedharan, Prathapan; Lindsey, Jonathan S.

2010-05-25

The present invention provides dipyrrin substituted porphyrinic macrocycles, intermediates useful for making the same, and methods of making the same. Such compounds may be used for purposes including the making of molecular memory devices, solar cells and light harvesting arrays.

Ultrafast excited-state dynamics of 2,5-dimethylpyrrole.

PubMed

Yang, Dongyuan; Min, Yanjun; Chen, Zhichao; He, Zhigang; Yuan, Kaijun; Dai, Dongxu; Yang, Xueming; Wu, Guorong

2018-04-17

The ultrafast excited-state dynamics of 2,5-dimethylpyrrole following excitation at wavelengths in the range of 265.7-216.7 nm is studied using the time-resolved photoelectron imaging method. It is found that excitation at longer wavelengths (265.7-250.2 nm) results in the population of the S1(1πσ*) state, which decays out of the photoionization window in about 90 fs. At shorter pump wavelengths (242.1-216.7 nm), the assignments are less clear-cut. We tentatively assign the initially photoexcited state(s) to the 1π3p Rydberg state(s) which has lifetimes of 159 ± 20, 125 ± 15, 102 ± 10 and 88 ± 10 fs for the pump wavelengths of 242.1, 238.1, 232.6 and 216.7 nm, respectively. Internal conversion to the S1(1πσ*) state represents at most a minor decay channel. The methyl substitution effects on the decay dynamics of the excited states of pyrrole are also discussed. Methyl substitution on the pyrrole ring seems to enhance the direct internal conversion from the 1π3p Rydberg state to the ground state, while methyl substitution on the N atom has less influence and the internal conversion to the S1(πσ*) state represents a main channel.

Magnetic moment directions and distributions of cations in Cr (Co) substituted spinel ferrites Ni0.7Fe2.3O4

NASA Astrophysics Data System (ADS)

Xue, L. C.; Lang, L. L.; Xu, J.; Li, Z. Z.; Qi, W. H.; Tang, G. D.; Wu, L. Q.

2015-09-01

Powder samples of the spinel ferrites MxNi0.7-xFe2.3O4 (M = Cr, Co and 0.0 ≤ x ≤ 0.3) and CrxNi0.7Fe2.3-xO4 (0.0 ≤ x ≤ 0.3) were synthesized using the chemical co-precipitation method. The XRD spectra confirmed that the samples had a single-phase cubic spinel structure. Magnetic measurements showed that the magnetic moments (μexp) per formula both at 10 K and 300 K increased with Co substitution, while the values of μexp decreased with Cr substitution. Applying the assumption that the magnetic moments of Cr2+ and Cr3+ lie antiparallel to those of the divalent and trivalent Fe, Co, and Ni cations in the same sublattice of spinel ferrites, these interesting behaviors could be easily interpreted. The cation distributions of the three series of samples were estimated successfully by fitting the dependences of μexp, measured at 10 K, on the doping level x, using a quantum-mechanical potential barrier model earlier proposed by our group. The results obtained for the Cr cation distributions at the (A) and [B] sites are very close to those obtained elsewhere using neutron diffraction.

Application of Mean of Absolute Deviation Method for the Selection of Best Nonlinear Component Based on Video Encryption

NASA Astrophysics Data System (ADS)

Anees, Amir; Khan, Waqar Ahmad; Gondal, Muhammad Asif; Hussain, Iqtadar

2013-07-01

The aim of this work is to make use of the mean of absolute deviation (MAD) method for the evaluation process of substitution boxes used in the advanced encryption standard. In this paper, we use the MAD technique to analyze some popular and prevailing substitution boxes used in encryption processes. In particular, MAD is applied to advanced encryption standard (AES), affine power affine (APA), Gray, Lui J., Residue Prime, S8 AES, SKIPJACK, and Xyi substitution boxes.

Electronic structure of Pt-substituted clathrate silicides Ba{sub 8}Pt{sub x}Si{sub 46–x}(x = 4–6)

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

Borshch, N. A., E-mail: n.a.borshch@ya.ru

The results of calculation of the electronic structure of Si-based Pt-substituted clathrates are reported. Calculation is carried out by the linearized-augmented-plane-wave method. The effect of the number of substitutions and their crystallographic position in the unit cell on the electron-energy spectrum and the electronic properties of Pt-substituted clathrates is analyzed.

Iterative key-residues interrogation of a phytase with thermostability increasing substitutions identified in directed evolution.

PubMed

Shivange, Amol V; Roccatano, Danilo; Schwaneberg, Ulrich

2016-01-01

Bacterial phytases have attracted industrial interest as animal feed supplement due to their high activity and sufficient thermostability (required for feed pelleting). We devised an approach named KeySIDE,  an iterative Key-residues interrogation of the wild type with Substitutions Identified in Directed Evolution for improving Yersinia mollaretii phytase (Ymphytase) thermostability by combining key beneficial substitutions and elucidating their individual roles. Directed evolution yielded in a discovery of nine positions in Ymphytase and combined iteratively to identify key positions. The "best" combination (M6: T77K, Q154H, G187S, and K289Q) resulted in significantly improved thermal resistance; the residual activity improved from 35 % (wild type) to 89 % (M6) at 58 °C and 20-min incubation. Melting temperature increased by 3 °C in M6 without a loss of specific activity. Molecular dynamics simulation studies revealed reduced flexibility in the loops located next to helices (B, F, and K) which possess substitutions (Helix-B: T77K, Helix-F: G187S, and Helix-K: K289E/Q). Reduced flexibility in the loops might be caused by strengthened hydrogen bonding network (e.g., G187S and K289E/K289Q) and a salt bridge (T77K). Our results demonstrate a promising approach to design phytases in food research, and we hope that the KeySIDE might become an attractive approach for understanding of structure-function relationships of enzymes.

Isotemporal Substitution Paradigm for Physical Activity Epidemiology and Weight Change

PubMed Central

Willett, Walter C.; Hu, Frank B.; Ding, Eric L.

2009-01-01

For a fixed amount of time engaged in physical activity, activity choice may affect body weight differently depending partly on other activities’ displacement. Typical models used to evaluate effects of physical activity on body weight do not directly address these substitutions. An isotemporal substitution paradigm was developed as a new analytic model to study the time-substitution effects of one activity for another. In 1991–1997, the authors longitudinally examined the associations of discretionary physical activities, with varying activity displacements, with 6-year weight loss maintenance among 4,558 healthy, premenopausal US women who had previously lost >5% of their weight. Results of isotemporal substitution models indicated widely heterogeneous relations with each physical activity type (P < 0.001) depending on the displaced activities. Notably, whereas 30 minutes/day of brisk walking substituted for 30 minutes/day of jogging/running was associated with weight increase (1.57 kg, 95% confidence interval: 0.33, 2.82), brisk walking was associated with lower weight when substituted for slow walking (−1.14 kg, 95% confidence interval: −1.75, −0.53) and with even lower weight when substituted for TV watching. Similar heterogeneous relations with weight change were found for each activity type (TV watching, slow walking, brisk walking, jogging/running) when displaced by other activities across these various models. The isotemporal substitution paradigm may offer new insights for future public health recommendations. PMID:19584129

Zinc and Carbonate Co-Substituted Nano-Hydroxyapatite

NASA Astrophysics Data System (ADS)

Girija, E. K.; Kumar, G. Suresh; Thamizhavel, A.

2011-07-01

Synthesis of Zn or CO32- substituted nano-hydroxyapatite (HA) and its physico-chemical properties have been well documented. However, the effects of the simultaneous substitution of Zn and CO32- in nano-HA have not been reported. In the present study, Zn and CO32- substitutions in nano HA independently and concurrently have been done by wet precipitation method and characterized by XRD and FT-IR for its phase purity and chemical homogeneity. Further modulations of the bioactivity and thermal stability of HA due to the substitutions have been studied.

Resorption behavior of a nanostructured bone substitute: in vitro investigation and clinical application.

PubMed

Reichert, Christoph; Götz, Werner; Reimann, Susanne; Keilig, Ludger; Hagner, Martin; Bourauel, Christoph; Jäger, Andreas

2013-03-01

To develop an in vitro assay for quantitative analysis of the degradation to which a bone substitute is exposed by osteoclasts. The aim of establishing this method was to improve the predictability of carrying out tooth movements via bone substitutes and to provide a basis for verification in exemplary clinical cases. After populating a bone substitute (NanoBone®; ArtOss, Germany) with osteoclastic cells, inductively-coupled mass spectrometry was used to evaluate changing calcium levels in the culture medium as a marker of resorption activity. It was observed that calcium levels increased substantially in the culture medium with the cells populating the bone substitute. This in vitro assay is a valid method that can assist clinicians in selecting the appropriate materials for certain patients. While tooth movements occurring through this material were successful, uncertainty about the approach will remain as long-term results are not available.

A Comparison of the β-Substitution Method and a Bayesian Method for Analyzing Left-Censored Data.

PubMed

Huynh, Tran; Quick, Harrison; Ramachandran, Gurumurthy; Banerjee, Sudipto; Stenzel, Mark; Sandler, Dale P; Engel, Lawrence S; Kwok, Richard K; Blair, Aaron; Stewart, Patricia A

2016-01-01

Classical statistical methods for analyzing exposure data with values below the detection limits are well described in the occupational hygiene literature, but an evaluation of a Bayesian approach for handling such data is currently lacking. Here, we first describe a Bayesian framework for analyzing censored data. We then present the results of a simulation study conducted to compare the β-substitution method with a Bayesian method for exposure datasets drawn from lognormal distributions and mixed lognormal distributions with varying sample sizes, geometric standard deviations (GSDs), and censoring for single and multiple limits of detection. For each set of factors, estimates for the arithmetic mean (AM), geometric mean, GSD, and the 95th percentile (X0.95) of the exposure distribution were obtained. We evaluated the performance of each method using relative bias, the root mean squared error (rMSE), and coverage (the proportion of the computed 95% uncertainty intervals containing the true value). The Bayesian method using non-informative priors and the β-substitution method were generally comparable in bias and rMSE when estimating the AM and GM. For the GSD and the 95th percentile, the Bayesian method with non-informative priors was more biased and had a higher rMSE than the β-substitution method, but use of more informative priors generally improved the Bayesian method's performance, making both the bias and the rMSE more comparable to the β-substitution method. An advantage of the Bayesian method is that it provided estimates of uncertainty for these parameters of interest and good coverage, whereas the β-substitution method only provided estimates of uncertainty for the AM, and coverage was not as consistent. Selection of one or the other method depends on the needs of the practitioner, the availability of prior information, and the distribution characteristics of the measurement data. We suggest the use of Bayesian methods if the practitioner has the computational resources and prior information, as the method would generally provide accurate estimates and also provides the distributions of all of the parameters, which could be useful for making decisions in some applications. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Polymeric medium

DOEpatents

Klaehn, John R [Idaho Falls, ID; Peterson, Eric S [Idaho Falls, ID; Orme, Christopher J [Shelley, ID; Jones, Michael G [Chubbuck, ID; Wertsching, Alan K [Idaho Falls, ID; Luther, Thomas A [Idaho Falls, ID; Trowbridge, Tammy L [Idaho Falls, ID

2012-03-06

A PBI compound includes imidazole nitrogens at least a portion of which are substituted with a moiety containing a carbonyl group, the substituted imidazole nitrogens being bonded to carbon of the carbonyl group. At least 85% of the nitrogens may be substituted. The carbonyl-containing moiety may include RCO--, where R is alkoxy or haloalkyl. The PBI compound may exhibit a first temperature marking an onset of weight loss corresponding to reversion of the substituted PBI that is less than a second temperature marking an onset of decomposition of an otherwise identical PBI compound without the substituted moiety. The PBI compound may be included in separatory media. A substituted PBI synthesis method may include providing a parent PBI in a less than 5 wt % solvent solution. Substituting may use more than 5 equivalents in relation to the imidazole nitrogens to be substituted.

Polybenzimidazole compounds

DOEpatents

Klaehn, John R [Idaho Falls, ID; Peterson, Eric S [Idaho Falls, ID; Orme, Christopher J [Shelley, ID; Jones, Michael G [Chubbuck, ID; Wertsching, Alan K [Idaho Falls, ID; Luther, Thomas A [Idaho Falls, ID; Trowbridge, Tammy L [Idaho Falls, ID

2011-11-22

A PBI compound includes imidazole nitrogens at least a portion of which are substituted with a moiety containing a carbonyl group, the substituted imidazole nitrogens being bonded to carbon of the carbonyl group. At least 85% of the nitrogens may be substituted. The carbonyl-containing moiety may include RCO--, where R is alkoxy or haloalkyl. The PBI compound may exhibit a first temperature marking an onset of weight loss corresponding to reversion of the substituted PBI that is less than a second temperature marking an onset of decomposition of an otherwise identical PBI compound without the substituted moiety. The PBI compound may be included in separatory media. A substituted PBI synthesis method may include providing a parent PBI in a less than 5 wt % solvent solution. Substituting may use more than 5 equivalents in relation to the imidazole nitrogens to be substituted.

Organ engineering--combining stem cells, biomaterials, and bioreactors to produce bioengineered organs for transplantation.

PubMed

Murphy, Sean Vincent; Atala, Anthony

2013-03-01

Often the only treatment available for patients suffering from diseased and injured organs is whole organ transplant. However, there is a severe shortage of donor organs for transplantation. The goal of organ engineering is to construct biological substitutes that will restore and maintain normal function in diseased and injured tissues. Recent progress in stem cell biology, biomaterials, and processes such as organ decellularization and electrospinning has resulted in the generation of bioengineered blood vessels, heart valves, livers, kidneys, bladders, and airways. Future advances that may have a significant impact for the field include safe methods to reprogram a patient's own cells to directly differentiate into functional replacement cell types. The subsequent combination of these cells with natural, synthetic and/or decellularized organ materials to generate functional tissue substitutes is a real possibility. This essay reviews the current progress, developments, and challenges facing researchers in their goal to create replacement tissues and organs for patients. Copyright © 2013 WILEY Periodicals, Inc.

Novel human CRYGD rare variant in a Brazilian family with congenital cataract

PubMed Central

Giordano, Gabriel Gorgone; Tavares, Anderson; da Silva, Márcio José; de Vasconcellos, José Paulo Cabral; Arieta, Carlos Eduardo Leite; de Melo, Mônica Barbosa

2011-01-01

Purpose To describe a novel polymorphism in the γD-crystallin (CRYGD) gene in a Brazilian family with congenital cataract. Methods A Brazilian four-generation family was analyzed. The proband had bilateral lamellar cataract and the phenotypes were classified by slit lamp examination. Genomic DNA was extracted from peripheral blood and coding regions and intron/exon boundaries of the αA-crystallin (CRYAA), γC-crystallin (CRYGC), and CRYGD genes were amplified by polymerase chain reaction and directly sequenced. Results Sequencing of the coding regions of CRYGD showed the presence of a heterozygous A→G transversion at c.401 position, which results in the substitution of a tyrosine to a cysteine (Y134C). The polymorphism was identified in three individuals, two affected and one unaffected. Conclusions A novel rare variant in CRYGD (Y134C) was detected in a Brazilian family with congenital cataract. Because there is no segregation between the substitution and the phenotypes in this family, other genetic alterations are likely to be present. PMID:21866214

Analysis on Potential of Electric Energy Market based on Large Industrial Consumer

NASA Astrophysics Data System (ADS)

Lin, Jingyi; Zhu, Xinzhi; Yang, Shuo; Xia, Huaijian; Yang, Di; Li, Hao; Lin, Haiying

2018-01-01

The implementation of electric energy substitution by enterprises plays an important role in promoting the development of energy conservation and emission reduction in china. In order to explore alternative energy potential of industrial enterprises, to simulate and analyze the process of industrial enterprises, identify high energy consumption process and equipment, give priority to alternative energy technologies, and determine the enterprise electric energy substitution potential predictive value, this paper constructs the evaluation model of the influence factors of the electric energy substitution potential of industrial enterprises, and uses the combined weight method to determine the weight value of the evaluation factors to calculate the target value of the electric energy substitution potential. Taking the iron and steel industry as an example, this method is used to excavate the potential. The results show that the method can effectively tap the potential of the electric power industry

Electrochemical systems and methods using metal halide to form products

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

Albrecht, Thomas A.; Solas, Dennis; Leclerc, Margarete K.

There are provided electrochemical methods and systems to form one or more organic compounds or enantiomers thereof selected from the group consisting of substituted or unsubstituted dioxane, substituted or unsubstituted dioxolane, dichloroethylether, dichloromethyl methyl ether, dichloroethyl methyl ether, chloroform, carbon tetrachloride, phosgene, and combinations thereof.

40 CFR Appendix B to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

Code of Federal Regulations, 2012 CFR

2012-07-01

... Analysis in Manufacturing and Assembly Processes (Process FMEA). Revised January 2009. SAE International. 3... submitted to demonstrate it can be used safely in this end-use. CFC-11, CFC-12, R-502 Industrial Process... Outside diameter of 20.955 +0/−0.127 mm (0.825 +0/−0.005 inches) and right-hand thread direction for CO2...

40 CFR Appendix H to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes, Effective May 28, 1999

Code of Federal Regulations, 2010 CFR

2010-07-01

... STRATOSPHERIC OZONE Significant New Alternatives Policy Program Pt. 82, Subpt. G, App. H Appendix H to Subpart G..., 1999 CFC-12 Automobile and Non-automobile Motor Vehicle Air Conditioners, Retrofit and New Criteria for... inch or the thread direction must be reversed (i.e. right-handed vs. left-handed). Simply changing the...

Proteorhodopsin in living color: diversity of spectral properties within living bacterial cells.

PubMed

Kelemen, Bradley R; Du, Mai; Jensen, Rasmus B

2003-12-03

Proteorhodopsin is a family of over 50 proteins that provide phototrophic capability to marine bacteria by acting as light-powered proton pumps. The potential importance of proteorhodopsin to global ocean ecosystems and the possible applications of proteorhodopsin in optical data storage and optical signal processing have spurred diverse research in this new family of proteins. We show that proteorhodopsin expressed in Escherichia coli is functional and properly inserted in the membrane. At high expression levels, it appears to self-associate. We present a method for determining spectral properties of proteorhodopsin in intact E. coli cells that matches results obtained with detergent-solubilized, purified proteins. Using this method, we observe distinctly different spectra for protonated and deprotonated forms of 21 natural proteorhodopsin proteins in intact E. coli cells. Upon protonation, the wavelength maxima red shifts between 13 and 53 nm. We find that pKa values between 7.1 and 8.5 describe the pH-dependent spectral shift for all of the 21 natural variants of proteorhodopsin. The wavelength maxima of the deprotonated forms of the 21 natural proteorhodopsins cluster in two sequence-related groups: blue proteorhodopsins (B-PR) and green proteorhodopsins (G-PR). The site-directed substitution Leu105Gln in Bac31A8 proteorhodopsin shifts this G-PR's wavelength maximum to a wavelength maximum the same as that of the B-PR Hot75m1 proteorhodopsin. The site-directed substitution Gln107Leu in Hot75m1 proteorhodopsin shifts this B-PR's wavelength maximum to a wavelength maximum as that of Bac31A8 proteorhodopsin.

Molecular methods for the detection of mutations.

PubMed

Monteiro, C; Marcelino, L A; Conde, A R; Saraiva, C; Giphart-Gassler, M; De Nooij-van Dalen, A G; Van Buuren-van Seggelen, V; Van der Keur, M; May, C A; Cole, J; Lehmann, A R; Steinsgrimsdottir, H; Beare, D; Capulas, E; Armour, J A

2000-01-01

We report the results of a collaborative study aimed at developing reliable, direct assays for mutation in human cells. The project used common lymphoblastoid cell lines, both with and without mutagen treatment, as a shared resource to validate the development of new molecular methods for the detection of low-level mutations in the presence of a large excess of normal alleles. As the "gold standard, " hprt mutation frequencies were also measured on the same samples. The methods under development included i) the restriction site mutation (RSM) assay, in which mutations lead to the destruction of a restriction site; ii) minisatellite length-change mutation, in which mutations lead to alleles containing new numbers of tandem repeat units; iii) loss of heterozygosity for HLA epitopes, in which antibodies can be used to direct selection for mutant cells; iv) multiple fluorescence-based long linker arm nucleotides assay (mf-LLA) technology, for the detection of substitutional mutations; v) detection of alterations in the TP53 locus using a (CA) array as the target for the screening; and vi) PCR analysis of lymphocytes for the presence of the BCL2 t(14:18) translocation. The relative merits of these molecular methods are discussed, and a comparison made with more "traditional" methods.

A visible light photocatalyst: effects of vanadium substitution on ETS-10.

PubMed

Marie Shough, Anne; Lobo, Raul F; Doren, Douglas J

2007-10-07

Hybrid density functional theory/molecular mechanics (DFT/MM) methods have been used to investigate the effects of vanadium substitution in ETS-10. Models have been developed to contain varying concentrations of V(IV) and V(V) within the O-M-O (M = Ti, V) chain. Most of the V-substituted models have a localized mid-gap state. The occupation of this localized state depends upon the dopant oxidation state, leading to the addition of multiple low energy transitions. A linear correlation has been identified between band gap energies estimated using ground state orbital energies and those calculated using the more accurate and computationally demanding time-dependent DFT (TDDFT) method for a variety of transition metal substituted models of ETS-10. Consistent with experimental data for V substitution, our models predict a decrease in the optical band gap with increasing [V], due to a lowering of the delocalized d-orbital states at the bottom of the conduction band with increasing V d-orbital character. This effect is more pronounced in the case of V(V) substitution than V(IV). Excitation energies for the V-doped models, calculated with TDDFT methods correlate well with experimental data, allowing for the assignment of specific optical transitions to experimental UV-Vis spectra. The electronic structure of V-substituted ETS-10 at high V concentration demonstrates band gap energies within the visible range of the spectrum. Additionally, at high [V] the band gap energy and presence of low energy electron traps can be controlled by the relative concentration of V(IV) and V(V) along the O-M-O chain, establishing V-substituted ETS-10 as a promising visible light photocatalyst.

Fabricating data: How substituting values for nondetects can ruin results, and what can be done about it

USGS Publications Warehouse

Helsel, D.R.

2006-01-01

The most commonly used method in environmental chemistry to deal with values below detection limits is to substitute a fraction of the detection limit for each nondetect. Two decades of research has shown that this fabrication of values produces poor estimates of statistics, and commonly obscures patterns and trends in the data. Papers using substitution may conclude that significant differences, correlations, and regression relationships do not exist, when in fact they do. The reverse may also be true. Fortunately, good alternative methods for dealing with nondetects already exist, and are summarized here with references to original sources. Substituting values for nondetects should be used rarely, and should generally be considered unacceptable in scientific research. There are better ways.

Effect of Gallium and Indium Co-Substituting on Upconversion Properties of Er/Yb:Yttrium Aluminum Garnet Powders Prepared by the Co-Precipitation Method.

PubMed

Zhang, Wei; Liang, Yun-Ling; Hu, Zheng-Fa; Feng, Zu-Yong; Lun, Ma; Zhang, Xiu-ping; Sheng, Xia; Liu, Qian; Luo, Jie

2016-04-01

Gallium and Indium co-substituted Yb, Er:YAG was fabricated through the chemical co-precipitation method. The formation process and structure of the Ga3+ and In3+ substituted phosphor powders were characterized by the X-ray diffraction, thermo-gravimetry analyzer, infrared spectra, and X-ray photoelectron spectroscopy, and the effects of Ga3+ and In3+ concentration on the luminescence properties were investigated by spectrum. The results showed that the blue shift occurred after the substitution of Ga3+ and In3+ for Al3+ in matrix, and the intensity of emission spectrum was affected by the concentration of Ga3+ and In3+.

Improved Methods to Produce Tissue-Engineered Skin Substitutes Suitable for the Permanent Closure of Full-Thickness Skin Injuries

PubMed Central

Larouche, Danielle; Cantin-Warren, Laurence; Desgagné, Maxime; Guignard, Rina; Martel, Israël; Ayoub, Akram; Lavoie, Amélie; Gauvin, Robert; Auger, François A.; Moulin, Véronique J.; Germain, Lucie

2016-01-01

Abstract There is a clinical need for skin substitutes to replace full-thickness skin loss. Our group has developed a bilayered skin substitute produced from the patient's own fibroblasts and keratinocytes referred to as Self-Assembled Skin Substitute (SASS). After cell isolation and expansion, the current time required to produce SASS is 45 days. We aimed to optimize the manufacturing process to standardize the production of SASS and to reduce production time. The new approach consisted in seeding keratinocytes on a fibroblast-derived tissue sheet before its detachment from the culture plate. Four days following keratinocyte seeding, the resulting tissue was stacked on two fibroblast-derived tissue sheets and cultured at the air–liquid interface for 10 days. The resulting total production time was 31 days. An alternative method adapted to more contractile fibroblasts was also developed. It consisted in adding a peripheral frame before seeding fibroblasts in the culture plate. SASSs produced by both new methods shared similar histology, contractile behavior in vitro and in vivo evolution after grafting onto mice when compared with SASSs produced by the 45-day standard method. In conclusion, the new approach for the production of high-quality human skin substitutes should allow an earlier autologous grafting for the treatment of severely burned patients. PMID:27872793

No-carrier-added (NCA) aryl ([sup 18]F) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

DOEpatents

Yushin Ding; Fowler, J.S.; Wolf, A.P.

1993-10-19

A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

No-carrier-added (NCA) aryl (18E) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

DOEpatents

Ding, Yu-Shin; Fowler, Joanna S.; Wolf, Alfred P.

1993-01-01

A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

Field substitution of nonresponders can maintain sample size and structure without altering survey estimates-the experience of the Italian behavioral risk factors surveillance system (PASSI).

PubMed

Baldissera, Sandro; Ferrante, Gianluigi; Quarchioni, Elisa; Minardi, Valentina; Possenti, Valentina; Carrozzi, Giuliano; Masocco, Maria; Salmaso, Stefania

2014-04-01

Field substitution of nonrespondents can be used to maintain the planned sample size and structure in surveys but may introduce additional bias. Sample weighting is suggested as the preferable alternative; however, limited empirical evidence exists comparing the two methods. We wanted to assess the impact of substitution on surveillance results using data from Progressi delle Aziende Sanitarie per la Salute in Italia-Progress by Local Health Units towards a Healthier Italy (PASSI). PASSI is conducted by Local Health Units (LHUs) through telephone interviews of stratified random samples of residents. Nonrespondents are replaced with substitutes randomly preselected in the same LHU stratum. We compared the weighted estimates obtained in the original PASSI sample (used as a reference) and in the substitutes' sample. The differences were evaluated using a Wald test. In 2011, 50,697 units were selected: 37,252 were from the original sample and 13,445 were substitutes; 37,162 persons were interviewed. The initially planned size and demographic composition were restored. No significant differences in the estimates between the original and the substitutes' sample were found. In our experience, field substitution is an acceptable method for dealing with nonresponse, maintaining the characteristics of the original sample without affecting the results. This evidence can support appropriate decisions about planning and implementing a surveillance system. Copyright © 2014 Elsevier Inc. All rights reserved.

A simple modification of the Baermann method for diagnosis of strongyloidiasis.

PubMed

Hernández-Chavarría, F; Avendaño, L

2001-08-01

The diagnosis of Strongyloides stercoralis infections is routinely made by microscopic observation of larvae in stool samples, a low sensitivity method, or by other, most effective methods, such as the Baermann or agar culture plate methods. We propose in this paper a practical modification of Baermann method. One hundred and six stool samples from alcoholic patients were analyzed using the direct smear test, agar culture plate method, the standard Baermann method, and its proposed modification. For this modification the funnel used in the original version of the method is substituted by a test tube with a rubber stopper, perforated to allow insertion of a pipette tip. The tube with a fecal suspension is inverted over another tube containing 6 ml of saline solution and incubated at 37 degrees C for at least 2 h. The saline solution from the second tube is centrifuged and the pellet is observed microscopically. Larva of S. stercoralis were detected in six samples (5.7%) by the two versions of the Baermann method. Five samples were positive using the agar culture plate method, and only in two samples the larva were observed using direct microscopic observation of fecal smears. Cysts of Endolimax nana and Entamoeba histolytica/dyspar were also detected in the modification of Baermann method. Data obtained by the modified Baermann method suggest that this methodology may helps concentrate larvae of S. stercoralis as efficiently as the original method.

Imidazoline phosphonic acids

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

Redmore, D.

1972-07-04

Nitrogen-heterocyclic phosphonic acids and derivatives are characterized by aminomethyl (or substituted methyl) phosphonic acids or derivatives thereof bonded directly or indirectly, i.e., through a N-side chain to the nitrogen atom in the heterocyclic ring, for example those containing in the molecule at least one of the following units: ..pi..Equation/sup -/ where represents a heterocyclic ring having a nitrogen atom on the ring; -R'N- represents an amino- terminated side chain attached directly to the ring nitrogen (which side chain may or may not be present); and ..pi..Equation/sup -/ represents a methyl (or substituted methyl) phosphonic acid group where M is hydrogen,more » an alcohol or a salt moiety, and X and Y are hydrogen or a substituted group such as alkyl, aryl, etc., of which one or 2 units may be present depending on the available nitrogen bonded by hydrogens, and to uses for these compounds, for example, as scale inhibitors, corrosion inhibitors, etc. (5 claims)« less

Steric Effects of Solvent Molecules on SN2 Substitution Dynamics.

PubMed

Liu, Xu; Xie, Jing; Zhang, Jiaxu; Yang, Li; Hase, William L

2017-04-20

Influences of solvent molecules on S N 2 reaction dynamics of microsolvated F - (H 2 O) n with CH 3 I, for n = 0-3, are uncovered by direct chemical dynamics simulations. The direct substitution mechanism, which is important without microsolvation, is quenched dramatically upon increasing hydration. The water molecules tend to force reactive encounters to proceed through the prereaction collision complex leading to indirect reaction. In contrast to F - (H 2 O), reaction with higher hydrated ions shows a strong propensity for ion desolvation in the entrance channel, diminishing steric hindrance for nucleophilic attack. Thus, nucleophilic substitution avoids the potential energy barrier with all of the solvent molecules intact and instead occurs through the less solvated barrier, which is energetically unexpected because the former barrier has a lower energy. The work presented here reveals a trade-off between reaction energetics and steric effects, with the latter found to be crucial in understanding how hydration influences microsolvated S N 2 dynamics.

Arenium ions are not obligatory intermediates in electrophilic aromatic substitution

PubMed Central

Galabov, Boris; Koleva, Gergana; Simova, Svetlana; Hadjieva, Boriana; Schaefer, Henry F.; Schleyer, Paul von Ragué

2014-01-01

Our computational and experimental investigation of the reaction of anisole with Cl2 in nonpolar CCl4 solution challenges two fundamental tenets of the traditional SEAr (arenium ion) mechanism of aromatic electrophilic substitution. Instead of this direct substitution process, the alternative addition–elimination (AE) pathway is favored energetically. This AE mechanism rationalizes the preferred ortho and para substitution orientation of anisole easily. Moreover, neither the SEAr nor the AE mechanisms involve the formation of a σ-complex (Wheland-type) intermediate in the rate-controlling stage. Contrary to the conventional interpretations, the substitution (SEAr) mechanism proceeds concertedly via a single transition state. Experimental NMR investigations of the anisole chlorination reaction course at various temperatures reveal the formation of tetrachloro addition by-products and thus support the computed addition–elimination mechanism of anisole chlorination in nonpolar media. The important autocatalytic effect of the HCl reaction product was confirmed by spectroscopic (UV-visible) investigations and by HCl-augmented computational modeling. PMID:24972792

Site-directed mutagenesis of the conserved Asp-443 and Asp-498 carboxy-terminal residues of HIV-1 reverse transcriptase.

PubMed Central

Mizrahi, V; Usdin, M T; Harington, A; Dudding, L R

1990-01-01

Substitution of the conserved Asp-443 residue of HIV-1 reverse transcriptase by asparagine specifically suppressed the ribonuclease H activity of the enzyme without affecting the reverse transcriptase activity, suggesting involvement of this ionizable residue at the ribonuclease H active site. An analogous asparagine substitution of the Asp-498 residue yielded an unstable enzyme that was difficult to enzymatically characterize. However, the instability caused by the Asn-498 mutation was relieved by the introduction of a second distal Asn-443 substitution, yielding an enzyme with wild type reverse transcriptase activity, but lacking ribonuclease H activity. Images PMID:1699202

Transition-Metal Substitution Doping in Synthetic Atomically Thin Semiconductors

DOE PAGES

Gao, Jian; Kim, Young Duck; Liang, Liangbo; ...

2016-09-20

Semiconductor impurity doping has enabled an entire generation of technology. The emergence of alternative semiconductor material systems, such as transition metal dichalcogenides (TMDCs), requires the development of scalable doping strategies. We report an unprecedented one-pot synthesis for transition-metal substitution in large-area, synthetic monolayer TMDCs. Electron microscopy, optical and electronic transport characterization and ab initio calculations indicate that our doping strategy preserves the attractive qualities of TMDC monolayers, including semiconducting transport and strong direct-gap luminescence. These results are expected to encourage exploration of transition-metal substitution in two-dimensional systems, potentially enabling next-generation optoelectronic technology in the atomically-thin regime.

Surgical training and the European Working Time Directive: The role of informal workplace learning.

PubMed

Giles, James A

2010-01-01

The introduction of European Working Time Directive, limiting doctors' working hours to 48 per week, has caused recent controversy within the profession. The Royal College of Surgeons of England in particular has been one of the loudest critics of the legislation. One of the main concerns is regarding the negative impact on training hours for those embarking on surgical careers. Simulation technology has been suggested as a method to overcome this reduction in hospital training hours, and research suggests that this is a good substitute for operative training in a theatre. However, modern educational theory emphasises the power of informal workplace learning in postgraduate education, and the essential role of experience in training future surgeons. Copyright 2010 Surgical Associates Ltd. Published by Elsevier Ltd. All rights reserved.

Approaches to cutaneous wound healing: basics and future directions.

PubMed

Zeng, Ruijie; Lin, Chuangqiang; Lin, Zehuo; Chen, Hong; Lu, Weiye; Lin, Changmin; Li, Haihong

2018-04-10

The skin provides essential functions, such as thermoregulation, hydration, excretion and synthesis of vitamin D. Major disruptions of the skin cause impairment of critical functions, resulting in high morbidity and death, or leave one with life-changing cosmetic damage. Due to the complexity of the skin, diverse approaches are needed, including both traditional and advanced, to improve cutaneous wound healing. Cutaneous wounds undergo four phases of healing. Traditional management, including skin grafts and wound dressings, is still commonly used in current practice but in combination with newer technology, such as using engineered skin substitutes in skin grafts or combining traditional cotton gauze with anti-bacterial nanoparticles. Various upcoming methods, such as vacuum-assisted wound closure, engineered skin substitutes, stem cell therapy, growth factors and cytokine therapy, have emerged in recent years and are being used to assist wound healing, or even to replace traditional methods. However, many of these methods still lack assessment by large-scale studies and/or extensive application. Conceptual changes, for example, precision medicine and the rapid advancement of science and technology, such as RNA interference and 3D printing, offer tremendous potential. In this review, we focus on the basics of wound treatment and summarize recent developments involving both traditional and hi-tech therapeutic methods that lead to both rapid healing and better cosmetic results. Future studies should explore a more cost-effective, convenient and efficient approach to cutaneous wound healing. Graphical abstract Combination of various materials to create advanced wound dressings.

INTERLABORATORY STUDY OF A THERMOSPRAY-LIQUID CHROMATOGRAPHIC/MASS SPECTROMETRIC METHOD FOR SELECTED N-METHYL CARBAMATES, N-METHYL CARBAMOYLOXIMES, AND SUBSTITUTED UREA PESTICIDES

EPA Science Inventory

A thermospray-liquid chromatographic/mass spectrometric (TS-LC/MS) method was evaluated in an interlaboratory study for determining 3 N-methyl carbamates (bendiocarb, carbaryl, and carbofuran), 3-N-methyl carbamoyloximes (aldicarb, methomyl, and oxamyl), 2 substituted urea pestic...

Bone substitutes: a review of their characteristics, clinical use, and perspectives for large bone defects management

PubMed Central

Fernandez de Grado, Gabriel; Keller, Laetitia; Idoux-Gillet, Ysia; Wagner, Quentin; Musset, Anne-Marie; Benkirane-Jessel, Nadia; Bornert, Fabien; Offner, Damien

2018-01-01

Bone replacement might have been practiced for centuries with various materials of natural origin, but had rarely met success until the late 19th century. Nowadays, many different bone substitutes can be used. They can be either derived from biological products such as demineralized bone matrix, platelet-rich plasma, hydroxyapatite, adjunction of growth factors (like bone morphogenetic protein) or synthetic such as calcium sulfate, tri-calcium phosphate ceramics, bioactive glasses, or polymer-based substitutes. All these substitutes are not suitable for every clinical use, and they have to be chosen selectively depending on their purpose. Thus, this review aims to highlight the principal characteristics of the most commonly used bone substitutes and to give some directions concerning their clinical use, as spine fusion, open-wedge tibial osteotomy, long bone fracture, oral and maxillofacial surgery, or periodontal treatments. However, the main limitations to bone substitutes use remain the management of large defects and the lack of vascularization in their central part, which is likely to appear following their utilization. In the field of bone tissue engineering, developing porous synthetic substitutes able to support a faster and a wider vascularization within their structure seems to be a promising way of research. PMID:29899969

Directly auto-transplanted mesenchymal stem cells induce bone formation in a ceramic bone substitute in an ectopic sheep model.

PubMed

Boos, Anja M; Loew, Johanna S; Deschler, Gloria; Arkudas, Andreas; Bleiziffer, Oliver; Gulle, Heinz; Dragu, Adrian; Kneser, Ulrich; Horch, Raymund E; Beier, Justus P

2011-06-01

Bone tissue engineering approaches increasingly focus on the use of mesenchymal stem cells (MSC). In most animal transplantation models MSC are isolated and expanded before auto cell transplantation which might be critical for clinical application in the future. Hence this study compares the potential of directly auto-transplanted versus in vitro expanded MSC with or without bone morphogenetic protein-2 (BMP-2) to induce bone formation in a large volume ceramic bone substitute in the sheep model. MSC were isolated from bone marrow aspirates and directly auto-transplanted or expanded in vitro and characterized using fluorescence activated cell sorting (FACS) and RT-PCR analysis before subcutaneous implantation in combination with BMP-2 and β-tricalcium phosphate/hydroxyapatite (β-TCP/HA) granules. Constructs were explanted after 1 to 12 weeks followed by histological and RT-PCR evaluation. Sheep MSC were CD29(+), CD44(+) and CD166(+) after selection by Ficoll gradient centrifugation, while directly auto-transplanted MSC-populations expressed CD29 and CD166 at lower levels. Both, directly auto-transplanted and expanded MSC, were constantly proliferating and had a decreasing apoptosis over time in vivo. Directly auto-transplanted MSC led to de novo bone formation in a heterotopic sheep model using a β-TCP/HA matrix comparable to the application of 60 μg/ml BMP-2 only or implantation of expanded MSC. Bone matrix proteins were up-regulated in constructs following direct auto-transplantation and in expanded MSC as well as in BMP-2 constructs. Up-regulation was detected using immunohistology methods and RT-PCR. Dense vascularization was demonstrated by CD31 immunohistology staining in all three groups. Ectopic bone could be generated using directly auto-transplanted or expanded MSC with β-TCP/HA granules alone. Hence BMP-2 stimulation might become dispensable in the future, thus providing an attractive, clinically feasible approach to bone tissue engineering. © 2011 The Authors Journal of Cellular and Molecular Medicine © 2011 Foundation for Cellular and Molecular Medicine/Blackwell Publishing Ltd.

Strengthening of bridges by post-tensioning using monostrands in substituted cable ducts

NASA Astrophysics Data System (ADS)

Klusáček, Ladislav; Svoboda, Adam

2017-09-01

Post-tensioning is suitable, reliable and durable method of strengthening existing engineering structures, especially bridges. The high efficiency of post-tensioning can be seen in many applications throughout the world. In this paper the method is extended by a structural system of substituted cable ducts, which allows for significantly widening application of prestressing so it’s convenient mostly for application on beam bridges or slab bridges (built in years 1920 - 1960). The method of substituted cable ducts is based on theoretical knowledge and technical procedures, which were made possible through the development in prestressing systems, particularly the development of prestressing tendons (monostrands) and encased anchorages, as well as progress in drilling technology. This technique is highly recommended due to minimization of interventions into the constructions, unseen method of cable arrangement and hence the absence of impact on appearance, which is appreciated not only in case of valuable historical structures but also in general. It is possible to summarise that posttensioning by monostrands in substituted cable ducts is a highly effective method of strengthening existing bridges in order to increase their load capacities in terms of current traffic load and to extend their service life.

Clinical potential of methylphenidate in the treatment of cocaine addiction: a review of the current evidence

PubMed Central

Dürsteler, Kenneth M; Berger, Eva-Maria; Strasser, Johannes; Caflisch, Carlo; Mutschler, Jochen; Herdener, Marcus; Vogel, Marc

2015-01-01

Background Cocaine use continues to be a public health problem, yet there is no proven effective pharmacotherapy for cocaine dependence. A promising approach to treating cocaine dependence may be agonist-replacement therapy, which is already used effectively in the treatment of opioid and tobacco dependence. The replacement approach for cocaine dependence posits that administration of a long-acting stimulant medication should normalize the neurochemical and behavioral perturbations resulting from chronic cocaine use. One potential medication to be substituted for cocaine is methylphenidate (MPH), as this stimulant possesses pharmacobehavioral properties similar to those of cocaine. Aim To provide a qualitative review addressing the rationale for the use of MPH as a cocaine substitute and its clinical potential in the treatment of cocaine dependence. Methods We searched MEDLINE for clinical studies using MPH in patients with cocaine abuse/dependence and screened the bibliographies of the articles found for pertinent literature. Results MPH, like cocaine, increases synaptic dopamine by inhibiting dopamine reuptake. The discriminative properties, reinforcing potential, and subjective effects of MPH and cocaine are almost identical and, importantly, MPH has been found to substitute for cocaine in animals and human volunteers under laboratory conditions. When taken orally in therapeutic doses, its abuse liability, however, appears low, which is especially true for extended-release MPH preparations. Though there are promising data in the literature, mainly from case reports and open-label studies, the results of randomized controlled trials have been disappointing so far and do not corroborate the use of MPH as a substitute for cocaine dependence in patients without attention deficit hyperactivity disorder. Conclusion Clinical studies evaluating MPH substitution for cocaine dependence have provided inconsistent findings. However, the negative findings may be explained by specific study characteristics, among them dosing, duration of treatment, or sample size. This needs to be considered when discussing the potential of MPH as replacement therapy for cocaine dependence. Finally, based on the results, we suggest possible directions for future research. PMID:26124696

Site-directed mutagenesis of Autographa californica nucleopolyhedrovirus (AcNPV) polyhedrin: effect on polyhedron structure.

PubMed

Bravo-Patiño, A; Ibarra, J E

2000-01-01

Amino acids Lys34, His36, and Phe37 were substituted by PCR-mediated, site-directed mutagenesis for three Trp's in the AcNPV polyhedrin sequence. Phase contrast microscopy revealed refringent, amorphous polyhedra in the nuclei of infected cells. Electron microscopy confirmed a great variation in form and size of the mutated polyhedra. Although crystallization of the mutated polyhedrin occurred, it was irregular within each polyhedron. Virion occlusion was also severely affected. Virions were partially occluded, or only one virion was occluded per polyhedron. Results suggest that the substitution of these three amino acids affected the morphology of polyhedra, the uniformity of crystallization within each polyhedron, and the virion occlusion.

Reductive dechlorination of polychlorinated biphenyls by zerovalent iron in subcritical water

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

Yak, H.K.; Wenclawiak, B.W.; Cheng, I.F.

1999-04-15

A method for remediation of PCB-contaminated soil and sediments is described that uses zerovalent iron as the dechlorination agent and subcritical water extraction (SWE) as the transporting medium. By using 100-mesh iron powder and SWE conditions of 250 C and 10 MPa on Aroclor 1260 for 1--8 h, the higher chlorine-substituted homologues were completely reduced to their lower substituted counterparts. The lower-substituted congeners were subsequently near-completely dechlorinated. The initial findings indicate that this technique may be a viable method for remediation of PCB-contaminated soil and sediments.

Impact of Gd3+/graphene substitution on the physical properties of magnesium ferrite nanocomposites

NASA Astrophysics Data System (ADS)

Ateia, Ebtesam E.; Mohamed, Amira T.; Elsayed, Kareem

2018-04-01

Magnesium nano ferrite with composition MgFe2O4, MgGd0.05Fe1.95O4 and MgFe2O4 - 5 wt% GO was synthesized using a citrate auto-combustion method. The crystal structure, morphology, and magnetic properties of the investigated samples were studied. High Resolution Transmission Electron Microscopy (HRTEM) images show that the substitution of small amounts of Gd3+/GO causes a considerable reduction of the grain size. Studies on the magnetic properties demonstrate that the coercivity of GO-substituted magnesium nano ferrites is enhanced from 72 Oe to 203 Oe and the magnetocrystalline anisotropy constant increases from 1171 to 3425 emu Oe/gm at 300 K. The direct effects of graphene on morphology, crystal structure as well as the magnetic properties reveal that the studied sample are suitable for turbidity color and removal. The magnetic entropy change is estimated from magnetization data using Maxwell relation. The calculated Curie temperature from the Curie-Weiss law and the maximum entropy change are in good agreement with each other. Based on UV diffuse reflectance spectroscopy studies, the optical band gaps are in the range of 1.4-2.15 eV. In addition, the combination of small particle size and good magnetic properties makes the investigated samples act as a potential candidates for superior catalysts, adsorbents, and electromagnetic wave absorbers.

Mutant DnaAs of Escherichia coli that are refractory to negative control

PubMed Central

Chodavarapu, Sundari; Felczak, Magdalena M.; Simmons, Lyle A.; Murillo, Alec; Kaguni, Jon M.

2013-01-01

DnaA is the initiator of DNA replication in bacteria. A mutant DnaA named DnaAcos is unusual because it is refractory to negative regulation. We developed a genetic method to isolate other mutant DnaAs that circumvent regulation to extend our understanding of mechanisms that control replication initiation. Like DnaAcos, one mutant bearing a tyrosine substitution for histidine 202 (H202Y) withstands the regulation exerted by datA, hda and dnaN (β clamp), and both DnaAcos and H202Y resist inhibition by the Hda-β clamp complex in vitro. Other mutant DnaAs carrying G79D, E244K, V303M or E445K substitutions are either only partially sensitive or refractory to inhibition by the Hda-β clamp complex in vitro but are responsive to hda expression in vivo. All mutant DnaAs remain able to interact directly with Hda. Of interest, both DnaAcos and DnaAE244K bind more avidly to Hda. These mutants, by sequestrating Hda, may limit its availability to regulate other DnaA molecules, which remain active to induce extra rounds of DNA replication. Other evidence suggests that a mutant bearing a V292M substitution hyperinitiates by escaping the effect of an unknown regulatory factor. Together, our results provide new insight into the mechanisms that regulate replication initiation in Escherichia coli. PMID:23990329

Mutant DnaAs of Escherichia coli that are refractory to negative control.

PubMed

Chodavarapu, Sundari; Felczak, Magdalena M; Simmons, Lyle A; Murillo, Alec; Kaguni, Jon M

2013-12-01

DnaA is the initiator of DNA replication in bacteria. A mutant DnaA named DnaAcos is unusual because it is refractory to negative regulation. We developed a genetic method to isolate other mutant DnaAs that circumvent regulation to extend our understanding of mechanisms that control replication initiation. Like DnaAcos, one mutant bearing a tyrosine substitution for histidine 202 (H202Y) withstands the regulation exerted by datA, hda and dnaN (β clamp), and both DnaAcos and H202Y resist inhibition by the Hda-β clamp complex in vitro. Other mutant DnaAs carrying G79D, E244K, V303M or E445K substitutions are either only partially sensitive or refractory to inhibition by the Hda-β clamp complex in vitro but are responsive to hda expression in vivo. All mutant DnaAs remain able to interact directly with Hda. Of interest, both DnaAcos and DnaAE244K bind more avidly to Hda. These mutants, by sequestrating Hda, may limit its availability to regulate other DnaA molecules, which remain active to induce extra rounds of DNA replication. Other evidence suggests that a mutant bearing a V292M substitution hyperinitiates by escaping the effect of an unknown regulatory factor. Together, our results provide new insight into the mechanisms that regulate replication initiation in Escherichia coli.

Substitute decision-making for adults with intellectual disabilities living in residential care: learning through experience.

PubMed

Dunn, Michael C; Clare, Isabel C H; Holland, Anthony J

2008-03-01

In the UK, current policies and services for people with mental disorders, including those with intellectual disabilities (ID), presume that these men and women can, do, and should, make decisions for themselves. The new Mental Capacity Act (England and Wales) 2005 (MCA) sets this presumption into statute, and codifies how decisions relating to health and welfare should be made for those adults judged unable to make one or more such decisions autonomously. The MCA uses a procedural checklist to guide this process of substitute decision-making. The personal experiences of providing direct support to seven men and women with ID living in residential care, however, showed that substitute decision-making took two forms, depending on the type of decision to be made. The first process, 'strategic substitute decision-making', paralleled the MCA's legal and ethical framework, whilst the second process, 'relational substitute decision-making', was markedly different from these statutory procedures. In this setting, 'relational substitute decision-making' underpinned everyday personal and social interventions connected with residents' daily living, and was situated within a framework of interpersonal and interdependent care relationships. The implications of these findings for residential services and the implementation of the MCA are discussed.

Density impact on performance of composite Si/graphite electrodes

DOE PAGES

Dufek, Eric J.; Picker, Michael; Petkovic, Lucia M.

2016-01-27

The ability of alkali-substituted binders for composite Si and graphite negative electrodes to minimize capacity fade for lithium ion batteries is investigated. Polymer films and electrodes are described and characterized by FTIR following immersion in electrolyte (1:2 EC:DMC) for 24 h. FTIR analysis following electrode formation displayed similar alkali-ion dependent shifts in peak location suggesting that changes in the vibrational structure of the binder are maintained after electrode formation. The Si and graphite composite electrodes prepared using the alkali-substituted polyacrylates were also exposed to electrochemical cycling and it has been found that the performance of the Na-substituted binder is superiormore » to a comparable density K-substituted system. However, in comparing performance across many different electrode densities attention needs to be placed on making comparisons at similar densities, as low density electrodes tend to exhibit lower capacity fade over cycling. This is highlighted by a 6% difference between a low density K-substituted electrode and a high density Na-substituted sample. As a result, this low variance between the two systems makes it difficult to quickly make a direct evaluation of binder performance unless electrode density is tightly controlled.« less

Substituted 6-nitroquipazines, methods of preparation, and methods of use

DOEpatents

Mathis, Jr., Chester A.; Biegon, Anat; Taylor, Scott E.; Enas, Joel D.

1994-01-01

Disclosed is a substituted 6-nitroquipazine of the formula ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each selected from the group consisting of H, Fl, CL, Br, I, CF.sub.3, CH.sub.2 CH.sub.2 F, CH.sub.3, CH.sub.2 CH.sub.3, and --CH(CH.sub.3).sub.2, and wherein one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is other than H. Also disclosed is a method for measurement of serotonin uptake sites in a sample, in which a radioligand is incubated with a sample and then the radioactivity of the radioligand bound to the sample is determined, utilizing a radio labeled substituted 6-nitroquipazine as the radioligand. Also disclosed is a method of manufacture and method of use.

A Bionic Polarization Navigation Sensor and Its Calibration Method.

PubMed

Zhao, Huijie; Xu, Wujian

2016-08-03

The polarization patterns of skylight which arise due to the scattering of sunlight in the atmosphere can be used by many insects for deriving compass information. Inspired by insects' polarized light compass, scientists have developed a new kind of navigation method. One of the key techniques in this method is the polarimetric sensor which is used to acquire direction information from skylight. In this paper, a polarization navigation sensor is proposed which imitates the working principles of the polarization vision systems of insects. We introduce the optical design and mathematical model of the sensor. In addition, a calibration method based on variable substitution and non-linear curve fitting is proposed. The results obtained from the outdoor experiments provide support for the feasibility and precision of the sensor. The sensor's signal processing can be well described using our mathematical model. A relatively high degree of accuracy in polarization measurement can be obtained without any error compensation.

Determination of stream reaeration coefficients by use of tracers

USGS Publications Warehouse

Kilpatrick, F.A.; Rathbun, R.E.; Yotsukura, N.; Parker, G.W.; DeLong, L.L.

1987-01-01

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes.Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed in which a radioactive tracer gas was injected into a stream--the tracer gas being desorbed from the stream inversely to how oxygen would be absorbed. The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas.This manual describes the slug-injection and constant-rate injection methods of performing gas-tracer desorption measurements. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, methods of injection, sampling and analysis, and computational techniques to compute desorption and reaeration coefficients.

A Bionic Polarization Navigation Sensor and Its Calibration Method

PubMed Central

Zhao, Huijie; Xu, Wujian

2016-01-01

The polarization patterns of skylight which arise due to the scattering of sunlight in the atmosphere can be used by many insects for deriving compass information. Inspired by insects’ polarized light compass, scientists have developed a new kind of navigation method. One of the key techniques in this method is the polarimetric sensor which is used to acquire direction information from skylight. In this paper, a polarization navigation sensor is proposed which imitates the working principles of the polarization vision systems of insects. We introduce the optical design and mathematical model of the sensor. In addition, a calibration method based on variable substitution and non-linear curve fitting is proposed. The results obtained from the outdoor experiments provide support for the feasibility and precision of the sensor. The sensor’s signal processing can be well described using our mathematical model. A relatively high degree of accuracy in polarization measurement can be obtained without any error compensation. PMID:27527171

Chemical Methods for the Direct Detection and Labeling of S-Nitrosothiols

PubMed Central

Bechtold, Erika

2012-01-01

Abstract Significance: Posttranslational modification of proteins through phosphorylation, glycosylation, and oxidation adds complexity to the proteome by reversibly altering the structure and function of target proteins in a highly controlled fashion. Recent Advances: The study of reversible cysteine oxidation highlights a role for this oxidative modification in complex signal transduction pathways. Nitric oxide (NO), and its respective metabolites (including reactive nitrogen species), participates in a variety of these cellular redox processes, including the reversible oxidation of cysteine to S-nitrosothiols (RSNOs). RSNOs act as endogenous transporters of NO, but also possess beneficial effects independent of NO-related signaling, which suggests a complex and versatile biological role. In this review, we highlight the importance of RSNOs as a required posttranslational modification and summarize the current methods available for detecting S-nitrosation. Critical Issues: Given the limitations of these indirect detection methods, the review covers recent developments toward the direct detection of RSNOs by phosphine-based chemical probes. The intrinsic properties that dictate this phosphine/RSNO reactivity are summarized. In general, RSNOs (both small molecule and protein) react with phosphines to yield reactive S-substituted aza-ylides that undergo further reactions leading to stable RSNO-based adducts. Future Directions: This newly explored chemical reactivity forms the basis of a number of exciting potential chemical methods for protein RSNO detection in biological systems. Antioxid. Redox Signal. 17, 981–991. PMID:22356122

Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

PubMed

Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

2015-12-18

The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

Calcium release in skinned muscle fibres of the toad by transverse tubule depolarization or by direct stimulation.

PubMed

Lamb, G D; Stephenson, D G

1990-04-01

1. Skeletal muscle fibres from the toad were mechanically skinned under paraffin oil and then bathed in a potassium HDTA solution (HDTA: hexamethylenediamine-tetraacetate) which mimicked the ionic composition of the myoplasm. 2. Rapid transient contractions could be triggered by substitution of K+ with Na+ (with no change of anion), which should have virtually no direct effect on the electrical polarization of the sarcoplasmic reticulum (SR) membrane. Up to thirty or more contractions could be evoked by repeated substitutions if there was sufficient 'repriming' time (about 30 s) between them; these rapid contractions were analagous to potassium contractures in intact fibres. 3. When the SR was not heavily loaded, substitution of potassium HDTA with choline chloride also produced a rapid, brief contraction. 4. All treatments designed to 'inactivate' the voltage sensor in the T-system invariably abolished the rapid contractions. Thus, rapid contractions were absent if (i) the T-system was permanently depolarized by pre-soaking the muscle in a high potassium solution with ouabain before skinning, (ii) a fibre was split rather than skinned, (iii) the T-system was temporarily depolarized by Na+ substitution immediately before choline chloride substitution, or vice versa, (iv) a skinned fibre was briefly exposed to saponin (50 micrograms/ml) to selectively disrupt the T-system membrane or (v) the muscle was pre-soaked in a solution with 1 mM-EGTA and no Ca2+ or Mg2+ before skinning. In contrast to (v), if 10 mM-Mg2+ was present in the EGTA solution before skinning, rapid contractions could be elicited, presumably because the presence of Mg2+ prevented the inactivation of the T-system voltage sensor in low [Ca2+]. 5. These results unequivocally demonstrate that (a) the T-system reseals and repolarizes after mechanical skinning under oil and (b) the fast contractions are produced by activation of the voltage sensor in the T-system. 6. When the SR had been heavily loaded, choline chloride substitution (but not Na+ substitution) could also induce an unphysiological, slow contraction ('second component'). In total contrast to the fast contraction, this slow component was unaffected by any of the treatments (i-v) above, indicating that it did not depend on activation of the voltage sensor in the T-system but resulted from a direct action of choline chloride on the SR.(ABSTRACT TRUNCATED AT 400 WORDS)

Calcium release in skinned muscle fibres of the toad by transverse tubule depolarization or by direct stimulation.

PubMed Central

Lamb, G D; Stephenson, D G

1990-01-01

1. Skeletal muscle fibres from the toad were mechanically skinned under paraffin oil and then bathed in a potassium HDTA solution (HDTA: hexamethylenediamine-tetraacetate) which mimicked the ionic composition of the myoplasm. 2. Rapid transient contractions could be triggered by substitution of K+ with Na+ (with no change of anion), which should have virtually no direct effect on the electrical polarization of the sarcoplasmic reticulum (SR) membrane. Up to thirty or more contractions could be evoked by repeated substitutions if there was sufficient 'repriming' time (about 30 s) between them; these rapid contractions were analagous to potassium contractures in intact fibres. 3. When the SR was not heavily loaded, substitution of potassium HDTA with choline chloride also produced a rapid, brief contraction. 4. All treatments designed to 'inactivate' the voltage sensor in the T-system invariably abolished the rapid contractions. Thus, rapid contractions were absent if (i) the T-system was permanently depolarized by pre-soaking the muscle in a high potassium solution with ouabain before skinning, (ii) a fibre was split rather than skinned, (iii) the T-system was temporarily depolarized by Na+ substitution immediately before choline chloride substitution, or vice versa, (iv) a skinned fibre was briefly exposed to saponin (50 micrograms/ml) to selectively disrupt the T-system membrane or (v) the muscle was pre-soaked in a solution with 1 mM-EGTA and no Ca2+ or Mg2+ before skinning. In contrast to (v), if 10 mM-Mg2+ was present in the EGTA solution before skinning, rapid contractions could be elicited, presumably because the presence of Mg2+ prevented the inactivation of the T-system voltage sensor in low [Ca2+]. 5. These results unequivocally demonstrate that (a) the T-system reseals and repolarizes after mechanical skinning under oil and (b) the fast contractions are produced by activation of the voltage sensor in the T-system. 6. When the SR had been heavily loaded, choline chloride substitution (but not Na+ substitution) could also induce an unphysiological, slow contraction ('second component'). In total contrast to the fast contraction, this slow component was unaffected by any of the treatments (i-v) above, indicating that it did not depend on activation of the voltage sensor in the T-system but resulted from a direct action of choline chloride on the SR.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:1696987

Evolution and Persistence of the Resistance-Associated Substitutions of Hepatitis C Virus after Direct-Acting Antiviral Treatment Failures.

PubMed

Jeong, Yechan; Jin, Bora; Lee, Hye Won; Park, Hye Jung; Park, Jun Yong; Kim, Do Young; Han, Kwang-Hyub; Ahn, Sang Hoon; Kim, Seungtaek

2018-05-16

Daclatasvir plus asunaprevir (DCV+ASV) treatment is an all-oral direct-acting antiviral (DAA) therapy for the genotype 1b HCV-infected patients. In this study, we investigated how resistance-associated substitutions (RASs) evolved after treatment failures and assessed the effect of those substitutions on viral fitness. Sequencing of NS5A and NS3 revealed typical RASs after treatment failures. Interestingly, the RASs of NS3 reverted to the wild-type amino acid within one year after treatment failures. However, the RASs of NS5A were stable and did not change. The effect of NS5A and NS3 RASs on viral RNA replication was assessed after mutagenic substitution in the genotype 1b HCV RNA. Among the single substitutions, the effect of D168V was more substantial than the others and the effect of the triple mutant combination (D168V+L31V+Y93H) was the most severe. The RAS at NS5A Y93 affected both viral RNA replication and virus production. Finally, the effect of trans-complementation of NS5A was demonstrated in our co-transfection experiments and these results suggest that such a trans-complementation effect of NS5A may help maintain the NS5A RASs for a long time even after cessation of the DAA treatment. In conclusion, the results from this investigation would help understand the emergence and persistence of RASs. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

A computational method for solving stochastic Itô–Volterra integral equations based on stochastic operational matrix for generalized hat basis functions

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

Heydari, M.H., E-mail: heydari@stu.yazd.ac.ir; The Laboratory of Quantum Information Processing, Yazd University, Yazd; Hooshmandasl, M.R., E-mail: hooshmandasl@yazd.ac.ir

2014-08-01

In this paper, a new computational method based on the generalized hat basis functions is proposed for solving stochastic Itô–Volterra integral equations. In this way, a new stochastic operational matrix for generalized hat functions on the finite interval [0,T] is obtained. By using these basis functions and their stochastic operational matrix, such problems can be transformed into linear lower triangular systems of algebraic equations which can be directly solved by forward substitution. Also, the rate of convergence of the proposed method is considered and it has been shown that it is O(1/(n{sup 2}) ). Further, in order to show themore » accuracy and reliability of the proposed method, the new approach is compared with the block pulse functions method by some examples. The obtained results reveal that the proposed method is more accurate and efficient in comparison with the block pule functions method.« less

Light-induced noncentrosymmetry in acceptor-donor-substituted azobenzene solutions

NASA Astrophysics Data System (ADS)

Zhao, Jiang; Si, Jinhai; Wang, Yougui; Ye, Peixian; Fu, Xingfa; Qiu, Ling; Shen, Yuquan

1995-10-01

Light-induced noncentrosymmetry was achieved experimentally in acceptor-donor-substituted azobenzene solutions and observed by phase-matched nondegenerate six-wave mixing. The microscopic origin of the induced noncentrosymmetry was found to be orientational hole burning, which was distinguished directly with net orientation of molecules by experimental observations. The decay time of the induced noncentrosymmetry depended on the rotational orientation time of the sample's molecule, which varied linearly with the viscosity of the solvent.

Pressure and phase dependence of the stereochemical course in hot tritium for hydrogen and chlorine-38 for chlorine substitution in meso- and rac-1,2-dichloro-1,2-difluoroethane

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

Machulla, H J; Stocklin, G

1974-03-28

The pressure dependence of the stereochemical course in hot homolytic T- for-H and /sup 38/ Cl-for-Cl substitution in mesoand rac-1,2-dichloro-l,2- difluoroethane has been studied from 10 to 10/sup 4/ Torr. Distinct differences are observed between the yield vs. density dependence of the retained and the inverted product. For both recoil tritium and chlorine, substitution with inversion of configuration is almost negligible in the gas phase and its yields remained constant over the entire pressure range studied. Typical pressure effects are observed, however, for substitution with retention of configuration, particularly for recoil chlorine. While the change from the high-pressure gas phasemore » to the liquid leaves T-for-H substitution almost unaffected, /sup 38/Cl-for- Cl substitution exhibits a strong phase effect. The absolute yields of the retained product increase by a factor of 2.5, that of the invented product by about 20, almost identical in both diastereomeric substrates. The density dependence of the HCl and HF elimination products is also different for recoil tritium and chlorine; in the latter case the yields follow the increasing trend observed for substitution. While for recoil tritium the predominant substitution channel seems to be a direct replacement with retention of configuration, even in the liquid phase, /sup 38/Cl-for-Cl substitution at higher densities cannot be satisfactorily explained on the basis of the impact model nor by caged radical combination. Alternatively, substitution via a caged complex is discussed. (auth)« less

Amino acid substitutions in random mutagenesis libraries: lessons from analyzing 3000 mutations.

PubMed

Zhao, Jing; Frauenkron-Machedjou, Victorine Josiane; Kardashliev, Tsvetan; Ruff, Anna Joëlle; Zhu, Leilei; Bocola, Marco; Schwaneberg, Ulrich

2017-04-01

The quality of amino acid substitution patterns in random mutagenesis libraries is decisive for the success in directed evolution campaigns. In this manuscript, we provide a detailed analysis of the amino acid substitutions by analyzing 3000 mutations of three random mutagenesis libraries (1000 mutations each; epPCR with a low-mutation and a high-mutation frequency and SeSaM-Tv P/P) employing lipase A from Bacillus subtilis (bsla). A comparison of the obtained numbers of beneficial variants in the mentioned three random mutagenesis libraries with a site saturation mutagenesis (SSM) (covering the natural diversity at each amino acid position of BSLA) concludes the diversity analysis. Seventy-six percent of the SeSaM-Tv P/P-generated substitutions yield chemically different amino acid substitutions compared to 64% (epPCR-low) and 69% (epPCR-high). Unique substitutions from one amino acid to others are termed distinct amino acid substitutions. In the SeSaM-Tv P/P library, 35% of all theoretical distinct amino acid substitutions were found in the 1000 mutation library compared to 25% (epPCR-low) and 26% (epPCR-high). Thirty-six percent of distinct amino acid substitutions found in SeSaM-Tv P/P were unobtainable by epPCR-low. Comparison with the SSM library showed that epPCR-low covers 15%, epPCR-high 18%, and SeSaM-Tv P/P 21% of obtainable beneficial amino acid positions. In essence, this study provides first insights on the quality of epPCR and SeSaM-Tv P/P libraries in terms of amino acid substitutions, their chemical differences, and the number of obtainable beneficial amino acid positions.

Nutrient-substituted hydroxyapatites: synthesis and characterization

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.

1999-01-01

Incorporation of Mg, S, and plant-essential micronutrients into the structure of synthetic hydroxyapatite (HA) may be advantageous for closed-loop systems, such as will be required on Lunar and Martian outposts, because these apatites can be used as slow-release fertilizers. Our objective was to synthesize HA with Ca, P, Mg, S, Fe, Cu, Mn, Zn, Mo, B, and Cl incorporated into the structure, i.e., nutrient-substituted apatites. Hydroxyapatite, carbonate hydroxyapatite (CHA), nutrient-substituted hydroxyapatite (NHA), and nutrient-substituted carbonate hydroxyapatite (NCHA) were synthesized by precipitating from solution. Chemical and mineralogical analysis of precipitated samples indicated a considerable fraction of the added cations were incorporated into HA, without mineral impurities. Particle size of the HA was in the 1 to 40 nm range, and decreased with increased substitution of nutrient elements. The particle shape of HA was elongated in the c-direction in unsubstituted HA and NHA but more spherical in CHA and NCHA. The substitution of cations and anions in the HA structure was confirmed by the decrease of the d[002] spacing of HA with substitution of ions with an ionic radius less than that of Ca or P. The DTPA-extractable Cu ranged from 8 to 8429 mg kg-1, Zn ranged from 57 to 1279 mg kg-1, Fe from 211 to 2573 mg kg-1, and Mn from 190 to 1719 mg kg-1, depending on the substitution level of each element in HA. Nutrient-substituted HA has the potential to be used as a slow-release fertilizer to supply micronutrients, S, and Mg in addition to Ca and P.

Substitution and addition reactions of •OH with p-substituted-phenols

NASA Astrophysics Data System (ADS)

Albarrán, Guadalupe; Galicia-Jiménez, Eduardo; Mendoza, Edith; Schuler, Robert H.

2017-04-01

The directing effect of a hydroxyl group on the substitution and addition reactions of •OH to the substituted and free positions in aromatic rings of p-substituted-phenols were studied in aqueous solutions containing either K3Fe(CN)6 as an oxidant of the substituted hydroxycyclohexadienyl radical initially formed or using ascorbic acid. The results showed that the attack of the •OH to the substituted position (ipso position) was followed by elimination of the substituent producing hydroquinone. The addition reaction of the •OH to the free position on the ring produced 4-substituent-catechol and 4-substituent-resorcinol derivatives. Identification and quantification of the radiolytic products were carried out using high performance liquid chromatography. The results of the yields are given for the p-halogen-phenols (p-X-Ph) p-F-Ph, p-Cl-Ph, p-Br-Ph and p-I-Ph. Other compounds, p-nitro-Ph, p-OH-benzoic acid, p-OH-benzonitrile, p-OH-benzaldehyde, p-OH-anisole and p-OH-benzyl alcohol (represented as p-Z-Ph), were only studied using K3Fe(CN)6 as the oxidant. The results show that the p-X-Ph are attacked by the •OH at the ipso position to the halogen in the proportion 1:0.53:0.46:0.11 for F>Cl>Br>I. The •OH attacked at the ipso position to the p-Z-Phs through a substitution reaction, which depended on the substituent group. Thus, the strongly deactivating groups produced less hydroquinone, indicating less substitution reaction than the strongly activating groups.

Electrochemical Reduction of Carbon Dioxide to Methanol by Direct Injection of Electrons into Immobilized Enzymes on a Modified Electrode.

PubMed

Schlager, Stefanie; Dumitru, Liviu Mihai; Haberbauer, Marianne; Fuchsbauer, Anita; Neugebauer, Helmut; Hiemetsberger, Daniela; Wagner, Annika; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

2016-03-21

We present results for direct bio-electrocatalytic reduction of CO2 to C1 products using electrodes with immobilized enzymes. Enzymatic reduction reactions are well known from biological systems where CO2 is selectively reduced to formate, formaldehyde, or methanol at room temperature and ambient pressure. In the past, the use of such enzymatic reductions for CO2 was limited due to the necessity of a sacrificial co-enzyme, such as nicotinamide adenine dinucleotide (NADH), to supply electrons and the hydrogen equivalent. The method reported here in this paper operates without the co-enzyme NADH by directly injecting electrons from electrodes into immobilized enzymes. We demonstrate the immobilization of formate, formaldehyde, and alcohol dehydrogenases on one-and-the-same electrode for direct CO2 reduction. Carbon felt is used as working electrode material. An alginate-silicate hybrid gel matrix is used for the immobilization of the enzymes on the electrode. Generation of methanol is observed for the six-electron reduction with Faradaic efficiencies of around 10%. This method of immobilization of enzymes on electrodes offers the opportunity for electrochemical application of enzymatic electrodes to many reactions in which a substitution of the expensive sacrificial co-enzyme NADH is desired. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sample substitution can be an acceptable data-collection strategy: the case of the Belgian Health Interview Survey.

PubMed

Demarest, Stefaan; Molenberghs, Geert; Van der Heyden, Johan; Gisle, Lydia; Van Oyen, Herman; de Waleffe, Sandrine; Van Hal, Guido

2017-11-01

Substitution of non-participating households is used in the Belgian Health Interview Survey (BHIS) as a method to obtain the predefined net sample size. Yet, possible effects of applying substitution on response rates and health estimates remain uncertain. In this article, the process of substitution with its impact on response rates and health estimates is assessed. The response rates (RR)-both at household and individual level-according to the sampling criteria were calculated for each stage of the substitution process, together with the individual accrual rate (AR). Unweighted and weighted health estimates were calculated before and after applying substitution. Of the 10,468 members of 4878 initial households, 5904 members (RRind: 56.4%) of 2707 households (RRhh: 55.5%) participated. For the three successive (matched) substitutes, the RR dropped to 45%. The composition of the net sample resembles the one of the initial samples. Applying substitution did not produce any important distorting effects on the estimates. Applying substitution leads to an increase in non-participation, but does not impact the estimations.

Electrotactile and vibrotactile displays for sensory substitution systems

NASA Technical Reports Server (NTRS)

Kaczmarek, Kurt A.; Webster, John G.; Bach-Y-rita, Paul; Tompkins, Willis J.

1991-01-01

Sensory substitution systems provide their users with environmental information through a human sensory channel (eye, ear, or skin) different from that normally used or with the information processed in some useful way. The authors review the methods used to present visual, auditory, and modified tactile information to the skin and discuss present and potential future applications of sensory substitution, including tactile vision substitution (TVS), tactile auditory substitution, and remote tactile sensing or feedback (teletouch). The relevant sensory physiology of the skin, including the mechanisms of normal touch and the mechanisms and sensations associated with electrical stimulation of the skin using surface electrodes (electrotactile, or electrocutaneous, stimulation), is reviewed. The information-processing ability of the tactile sense and its relevance to sensory substitution is briefly summarized. The limitations of current tactile display technologies are discussed.

Synthesis and characterization of strontium-substituted hydroxyapatite nanoparticles for bone regeneration.

PubMed

Frasnelli, Matteo; Cristofaro, Francesco; Sglavo, Vincenzo M; Dirè, Sandra; Callone, Emanuela; Ceccato, Riccardo; Bruni, Giovanna; Cornaglia, Antonia Icaro; Visai, Livia

2017-02-01

The production of stable suspensions of strontium-substituted hydroxyapatite (Sr-HA) nanopowders, as Sr ions vector for bone tissue regeneration, was carried out in the present work. Sr-HA nanopowders were synthesized via aqueous precipitation methods using Sr 2+ amount from 0 to 100mol% and were characterized by several complementary techniques such as solid-state Nuclear Magnetic Resonance spectroscopy, X-ray diffraction, Infrared spectroscopy, N 2 physisorption and Transmission Electron Microscopy. The substitution of Ca 2+ with Sr 2+ in HA is always isomorphic with gradual evolution between the two limit compositions (containing 100% Ca and 100% Sr), this pointing out the homogeneity of the synthesized nanopowders and the complete solubility of strontium in HA lattice. Strontium addition is responsible for an increasing c/a ratio in the triclinic unit cell. A significant variation of the nanopowders shape and dimension is also observed, a preferential growth along the c-axis direction being evident at higher strontium loads. Modifications in the local chemical environment of phosphate and hydroxyl groups in the apatite lattice are also observed. Stable suspensions were produced by dispersing the synthesized nanopowders in bovine serum albumin. Characterization by Dynamic Light Scattering and ζ-potential determination allowed to show that Ca 2+ →Sr 2+ substitution influences the hydrodynamic diameter, which is always twice the particles size determined by TEM, the nanoparticles being always negatively charged as a result from the albumin rearrangement upon the interaction with nanoparticles surface. The biocompatibility of the suspensions was studied in terms of cell viability, apoptosis, proliferation and morphology, using osteosarcoma cell line SAOS-2. The data pointed out an increased cell proliferation for HA nanoparticles containing larger Sr 2+ load, the cells morphology remaining essentially unaffected. Copyright © 2016 Elsevier B.V. All rights reserved.

Neural/Bayes network predictor for inheritable cardiac disease pathogenicity and phenotype.

PubMed

Burghardt, Thomas P; Ajtai, Katalin

2018-04-11

The cardiac muscle sarcomere contains multiple proteins contributing to contraction energy transduction and its regulation during a heartbeat. Inheritable heart disease mutants affect most of them but none more frequently than the ventricular myosin motor and cardiac myosin binding protein c (mybpc3). These co-localizing proteins have mybpc3 playing a regulatory role to the energy transducing motor. Residue substitution and functional domain assignment of each mutation in the protein sequence decides, under the direction of a sensible disease model, phenotype and pathogenicity. The unknown model mechanism is decided here using a method combing neural and Bayes networks. Missense single nucleotide polymorphisms (SNPs) are clues for the disease mechanism summarized in an extensive database collecting mutant sequence location and residue substitution as independent variables that imply the dependent disease phenotype and pathogenicity characteristics in 4 dimensional data points (4ddps). The SNP database contains entries with the majority having one or both dependent data entries unfulfilled. A neural network relating causes (mutant residue location and substitution) and effects (phenotype and pathogenicity) is trained, validated, and optimized using fulfilled 4ddps. It then predicts unfulfilled 4ddps providing the implicit disease model. A discrete Bayes network interprets fulfilled and predicted 4ddps with conditional probabilities for phenotype and pathogenicity given mutation location and residue substitution thus relating the neural network implicit model to explicit features of the motor and mybpc3 sequence and structural domains. Neural/Bayes network forecasting automates disease mechanism modeling by leveraging the world wide human missense SNP database that is in place and expanding. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Novel microinjector for carrying bone substitutes for bone regeneration in periodontal diseases.

PubMed

Tsai, Hsiao-Cheng; Li, Yi-Chen; Young, Tai-Horng; Chen, Min-Huey

2016-01-01

Traditionally, guide bone regeneration (GBR) was a widely used method for repairing bone lost from periodontal disease. There were some disadvantages associated with the GBR method, such as the need for a stable barrier membrane and a new creative cavity during the surgical process. To address these disadvantages, the purpose of this study was to evaluate a novel microinjector developed for dental applications. The microinjector was designed to carry bone graft substitutes to restore bone defects for bone regeneration in periodontal diseases. The device would be used to replace the GBR method. In this study, the injected force and ejected volume of substitutes (including air, water, and ethanol) were defined by Hooke's law (n = 3). The optimal particle size of bone graft substitutes was determined by measuring the recycle ratio of bone graft substitutes from the microinjector (n = 3). Furthermore, a novel agarose gel model was used to evaluate the feasibility of the microinjector. The current study found that the injected force was less than 0.4 N for obtaining the ejected volume of approximately 2 mL, and when the particle size of tricalcium phosphate (TCP) was smaller than 0.5 mm, 80% TCP could be ejected from the microinjector. Furthermore, by using an agarose model to simulate the periodontal soft tissue, it was also found that bone graft substitutes could be easily injected into the gel. The results confirmed the feasibility of this novel microinjector for dental applications to carry bone graft substitutes for the restoration of bone defects of periodontal disease. Copyright © 2015. Published by Elsevier B.V.

Vitreous Substitutes: The Present and the Future

PubMed Central

Caprani, Simona Maria; Airaghi, Giulia; Bartalena, Luigi; Testa, Francesco; Mariotti, Cesare; Porta, Giovanni; Simonelli, Francesca

2014-01-01

Vitreoretinal surgery has advanced in numerous directions during recent years. The removal of the vitreous body is one of the main characteristics of this surgical procedure. Several molecules have been tested in the past to fill the vitreous cavity and to mimic its functions. We here review the currently available vitreous substitutes, focusing on their molecular properties and functions, together with their adverse effects. Afterwards we describe the characteristics of the ideal vitreous substitute. The challenges facing every ophthalmology researcher are to reach a long-term intraocular permanence of vitreous substitute with total inertness of the molecule injected and the control of inflammatory reactions. We report new polymers with gelification characteristics and smart hydrogels representing the future of vitreoretinal surgery. Finally, we describe the current studies on vitreous regeneration and cell cultures to create new intraocular gels with optimal biocompatibility and rheological properties. PMID:24877085

Meat analogues: Health promising sustainable meat substitutes.

PubMed

Kumar, Pavan; Chatli, M K; Mehta, Nitin; Singh, Parminder; Malav, O P; Verma, Akhilesh K

2017-03-24

There is a scarcity of protein of high biological value due to rapid increase in the world population and limited natural resources. Meat is a good source of protein of high biological value but converting the vegetable protein into animal protein is not economical. There is a trend of production of healthy and delicious meat free food for satisfaction of vegetarian and personal well beings. This resulted in increasing use of low cost vegetable protein such as textured soy protein, mushroom, wheat gluten, pulses etc as a substitute for animal-protein. These simulated meat-like products, with similar texture, flavor, color, and nutritive value can be substituted directly for meat to all sections of the society.

Immunoelectron Microscopy of Cryofixed and Freeze-Substituted Plant Tissues.

PubMed

Takeuchi, Miyuki; Takabe, Keiji; Mineyuki, Yoshinobu

2016-01-01

Cryofixation and freeze-substitution techniques provide excellent preservation of plant ultrastructure. The advantage of cryofixation is not only in structural preservation, as seen in the smooth plasma membrane, but also in the speed in arresting cell activity. Immunoelectron microscopy reveals the subcellular localization of molecules within cells. Immunolabeling in combination with cryofixation and freeze-substitution techniques provides more detailed information on the immunoelectron-microscopic localization of molecules in the plant cell than can be obtained from chemically fixed tissues. Here, we introduce methods for immunoelectron microscopy of cryofixed and freeze-substituted plant tissues.

Generic and therapeutic substitutions in the UK: are they a good thing?

PubMed Central

Duerden, Martin G; Hughes, Dyfrig A

2010-01-01

There is considerable interest and debate concerning the place of generic substitution (switching from a brand to generic product); and on therapeutic substitution, that is, switching to a cheaper, but apparently equivalent, product, usually within the drug class. Generic substitution by pharmacists is standard practice in UK hospital settings, and is being proposed for implementation in primary care. Although most prescriptions are already written generically (83% in the community in England in 2008), there are still cost savings that could be made if generic medicines are substituted against prescriptions written by branded name or by getting prescribers to adhere to advice to prescribe generically. Therapeutic substitution is more contentious, as direct evidence to support equivalence is normally lacking. However, the price differential between established drugs whose patents have expired and for which generics are available and newer, branded medicines within the same therapeutic class, makes therapeutic substitution an attractive application of cost-minimization analysis for the more efficient use of healthcare resources. Here we explore the tension that exists between the clinical appropriateness and safety of switching from an individual patient perspective and the consideration of value for money which is required to maximize population health from a health service perspective. Although substitution may affect individual patients (such as, for instance, reduced adherence, increased potential for medication error), it might be a price worth paying given the opportunity cost associated with the use of medicines that are clinically no better than cheaper alternatives. PMID:20716231

Cyperus rotundus, a substitute for Aconitum heterophyllum: Studies on the Ayurvedic concept of Abhava Pratinidhi Dravya (drug substitution)

PubMed Central

Venkatasubramanian, Padma; Kumar, Subrahmanya K; Nair, Venugopalan S. N.

2010-01-01

In the absence of a desired first choice medicinal herb, classical Ayurveda recommends use of a functionally similar substitute. Post 16th century Ayurvedic texts and lexicons give specific examples of possible substitutes. Here we report a preliminary study of one such Ayurvedic substitution pair: Musta (Cyperus rotundus L., Cyperaceae), a common weed, for the rare Himalayan species, Ativisha (Aconitum heterophyllum Wall. ex Royle; Ranunculaceae). The study's strategy was to use modern phytochemical and pharmacological methods to test the two herbs for biochemical and metabolic similarities and differences, and literary studies to compare their Ayurvedic properties, a novel trans-disciplinary approach. No previous scientific paper has compared the two herbs’ bioactivities or chemical profiles. Despite being taxonomically unrelated, the first choice, but relatively unavailable (Abhava) plant, A. heterophyllum, and its substitute (Pratinidhi) C. rotundus, are not only similar in Ayurvedic pharmacology (Dravyaguna) profile, but also in phytochemical and anti-diarrheal properties. These observations indicate that Ayurveda may attach more importance to pharmacological properties of raw drugs than to their botanical classification. Further research into the nature of raw drugs named could open up new areas of medicinal plant classification, linking chemistry and bioactivity. Understanding the logic behind the Ayurvedic concept of Abhava Pratinidhi Dravya (drug substitution) could lead to new methods of identifying legitimate drug alternatives, and help solve industry's problems of crude drug shortage. PMID:21829299

Identification by random forest method of HLA class I amino acid substitutions associated with lower survival at day 100 in unrelated donor hematopoietic cell transplantation.

PubMed

Marino, S R; Lin, S; Maiers, M; Haagenson, M; Spellman, S; Klein, J P; Binkowski, T A; Lee, S J; van Besien, K

2012-02-01

The identification of important amino acid substitutions associated with low survival in hematopoietic cell transplantation (HCT) is hampered by the large number of observed substitutions compared with the small number of patients available for analysis. Random forest analysis is designed to address these limitations. We studied 2107 HCT recipients with good or intermediate risk hematological malignancies to identify HLA class I amino acid substitutions associated with reduced survival at day 100 post transplant. Random forest analysis and traditional univariate and multivariate analyses were used. Random forest analysis identified amino acid substitutions in 33 positions that were associated with reduced 100 day survival, including HLA-A 9, 43, 62, 63, 76, 77, 95, 97, 114, 116, 152, 156, 166 and 167; HLA-B 97, 109, 116 and 156; and HLA-C 6, 9, 11, 14, 21, 66, 77, 80, 95, 97, 99, 116, 156, 163 and 173. In all 13 had been previously reported by other investigators using classical biostatistical approaches. Using the same data set, traditional multivariate logistic regression identified only five amino acid substitutions associated with lower day 100 survival. Random forest analysis is a novel statistical methodology for analysis of HLA mismatching and outcome studies, capable of identifying important amino acid substitutions missed by other methods.

Novel products from starch based feedstocks

USDA-ARS?s Scientific Manuscript database

There has been progress in the utilization of starch as a partial replacement for petroleum based plastics, but it remains a poor direct substitute for plastics, and a moderate one for composites. Our research focuses on using polymers produced from direct fermentation such as poly(lactic acid) or m...

Imaging the Material Properties of Bone Specimens using Reflection-Based Infrared Microspectroscopy

PubMed Central

Acerbo, Alvin S.; Carr, G. Lawrence; Judex, Stefan; Miller, Lisa M.

2012-01-01

Fourier Transform InfraRed Microspectroscopy (FTIRM) is a widely used method for mapping the material properties of bone and other mineralized tissues, including mineralization, crystallinity, carbonate substitution, and collagen cross-linking. This technique is traditionally performed in a transmission-based geometry, which requires the preparation of plastic-embedded thin sections, limiting its functionality. Here, we theoretically and empirically demonstrate the development of reflection-based FTIRM as an alternative to the widely adopted transmission-based FTIRM, which reduces specimen preparation time and broadens the range of specimens that can be imaged. In this study, mature mouse femurs were plastic-embedded and longitudinal sections were cut at a thickness of 4 μm for transmission-based FTIRM measurements. The remaining bone blocks were polished for specular reflectance-based FTIRM measurements on regions immediately adjacent to the transmission sections. Kramers-Kronig analysis of the reflectance data yielded the dielectric response from which the absorption coefficients were directly determined. The reflectance-derived absorbance was validated empirically using the transmission spectra from the thin sections. The spectral assignments for mineralization, carbonate substitution, and collagen cross-linking were indistinguishable in transmission and reflection geometries, while the stoichiometric/non-stoichiometric apatite crystallinity parameter shifted from 1032 / 1021 cm−1 in transmission-based to 1035 / 1025 cm−1 in reflection-based data. This theoretical demonstration and empirical validation of reflection-based FTIRM eliminates the need for thin sections of bone and more readily facilitates direct correlations with other methods such nanoindentation and quantitative backscatter electron imaging (qBSE) from the same specimen. It provides a unique framework for correlating bone’s material and mechanical properties. PMID:22455306

Blood substitutes.

PubMed Central

Kostrzewska, E.

1976-01-01

With the development of modern methods of surgery, anaesthesia, and pre- and postoperative care the requirement for blood substitutes is continuously increasing. We present a review of the different blood substitutes which are already in clinical use or in an advanced stage of experimental investigation for possible practical administration. Our own clinical experience with dextrans and experimental studies on stroma-free haemoglobin and hydroxyethyl starch solutions are described. PMID:57736

A Note on Parameters of Random Substitutions by γ-Diagonal Matrices

NASA Astrophysics Data System (ADS)

Kang, Ju-Sung

Random substitutions are very useful and practical method for privacy-preserving schemes. In this paper we obtain the exact relationship between the estimation errors and three parameters used in the random substitutions, namely the privacy assurance metric γ, the total number n of data records, and the size N of transition matrix. We also demonstrate some simulations concerning the theoretical result.

Effect of bismuth substitution in strontium hexaferrite

NASA Astrophysics Data System (ADS)

Sahoo, M. R.; Kuila, S.; Sweta, K.; Barik, A.; Vishwakarma, P. N.

2018-05-01

Bismuth (Bi) substituted M-type strontium hexaferrite (Sr1-xBix Fe12O19, x=0 and 0.02) are synthesized by sol-gel auto combustion method. Powder X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) shows increase in lattice parameter and particle size (500 nm to 3 micron) respectively, for Bi substituted sample. Magnetization via M-H shows decrease in magnetic hardness for Bi substituted samples. M-T data for parent (x=0) sample shows an antiferromagnetic transition in the ZFC plot at 495 °C. This antiferromagnetic transition is replaced by a ferromagnetic transition for FCW measurement. Similar behavior is displayed by the Bi substituted sample with transition temperature reduced to 455 °C.

Oleoresin Capsicum has Potential as a Rodent Repellent in Direct Sedding Longleaf Pine

Treesearch

James P. Barnett

1998-01-01

Direct seeding of southern pines has been a versatile and inexpensive alternative to planting on many reforestation sites across the South. Successful direct seeding has required that seeds be coated with thiram to repel birds, and with endrin to repel rodents. Endrin, which is extremely toxic, is no longer produced in the United States. Therefore, a substitute is...

Lanthanide-Substituted Magnetite Nanoparticles Using a New Mixed Precursor Method by Thermoanaerobacter ethanolicus

NASA Astrophysics Data System (ADS)

Moon, J.; Roh, Y.; Yeary, L. W.; Lauf, R. J.; Phelps, T. J.

2006-12-01

A metal reducing bacterium, Thermoanaerobacter ethanolicus successfully converted the precursor of L (lanthanide)-mixed akaganeite (LxFe1-xOOH) phase to L-substituted magnetite (LyFe3-yO4) while avoiding the potentially toxic effects of soluble L-ions. Antibiotic elements, lanthanide (Nd, Gd, Tb, Ho, and Er)-substituted magnetites were produced by microbial fermentation using LxFe1-xOOH, where x was up to 0.02 which is equivalent to 0.72 mM. Combining lanthanides into the akaganeite precursor phase mitigated some of the toxicity when compared to the traditional method by using pure akaganeite and the dissolved L-salt form. This new technique showed that an upper limit of L-concentrations between 0.02 and 0.1 mM might suppress bacterial activity. At the equivalent L-cation mole fraction, the traditional method increased the concentration of soluble toxic L ions in the final media. The precursor method enabled production of microbially synthesized L- substituted magnetite with an L-concentration 36-fold greater than could be obtained when the lanthanides were added as soluble salts. These results were confirmed by protein assay. The increase of L-concentration in the magnetite evidently manipulates its physical properties such as decreasing Curie temperature and decreasing saturation magnetism of L-substituted magnetite. This mixed precursor method can therefore be used to extend the application for nanofermentation and other bacterial synthesis fields where there is a need for economically low-energy consumable microbial production of nanoscale materials that should involve toxic or inhibitory elements to bacterial growth.

Multiflavor streptavidin

DOEpatents

Reznik, Gabriel O.; Sano, Takeshi; Vajda, Sandor; Smith, Cassandra; Cantor, Charles

2002-01-01

Compounds and methods are described for producing streptavidin mutants with changed affinities. In particular, modifications to the sequence of the natural streptavidin gene is described to create amino acid substitutions resulting in greater affinity for biotin substitutes than for biotin.

Correlating valence state, site preference and co-substitution to the magnetoelastic properties of cobalt ferrite

NASA Astrophysics Data System (ADS)

Nlebedim, Cajetan; Jiles, David

2015-03-01

Understanding how to influence the physics of magnetism, especially the relationship between magnetic susceptibility and stress, can be very useful in designing non-contact stress and torque sensors using magnetoelastic materials. This is particularly important considering that materials rarely occur in states desirable for direct applications. In this work we show that the magnetoelastic properties of cobalt ferrite are strongly dependent on the valence states and site preferences of substituted cations. It was found that co-substitution of magnetic and non-magnetic cations, is key to achieving simultaneous improvement in magnetostriction amplitude and strain sensitivity to applied magnetic field. Nevertheless, Curie temperature decreased, irrespective of the valence state, site preference or co-substitution. This presentation will show why tetravalent Ge resulted in superior magnetostrictive properties compared to other tetravalent, trivalent and divalent cations substituted into the crystal lattice of cobalt ferrite. This work was supported by the U.S. DOE, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The research was performed at Ames Laboratory, operated for the USDoE by Iowa State University (Contract #DE-AC02-07CH11358).

Origin of anomalous giant dielectric performance in novel perovskite: Bi0.5−xLaxNa0.5−xLixTi1−yMyO3 (M = Mg2+, Ga3+)

PubMed Central

Liu, Xiao; Fan, Huiqing; Shi, Jing; Li, Qiang

2015-01-01

Dielectric properties and dielectric relaxation behaviors of A/B sites co-substituted Bi0.5Na0.5TiO3 perovskite-type ferroelectrics are reported. The Bi0.5−xLaxNa0.5−xLixTi1−yMyO3 (M = Mg2+, Ga3+) exhibits anomalous giant dielectric permittivity (ε’) of ~105 under a heterogeneous constitution with easily discernible grain and grain boundary conductivity. The lone pairs substitution theory as well as extrinsic disorders are used to clarify the significant structural evolution and the origin of the dielectric performance. A bigger free volume promotes the anomalous relaxation between oxygen sites, and the polarization direction on the nanoscale deviates from the average polarization direction at its ferroelectric state. Furthermore, no obvious phase transition indicates the considerable static substitutional disorder at the Bi/Na sites, which facilitates delocalized conduction of oxygen ions in the intermediate temperature range. PMID:26239525

[The skin substitute center--a need in the treatment of patients with severe burns].

PubMed

Pieptu, D; Luchian, S

1999-01-01

The treatment of the severe burned patient has two main dimensions acting in an interdependent manner. First it is the life keeping and the second is skin resurfacing in a fair period of time. The failure of one of these two components leads to the patient's death. In the absence of the autografts the skin resurfacing has to be made by permanent skin substitutes--cultured epithelium, dermal equivalents or reconstructed skin, developed by a special unit, a Skin Substitute Center. The paper is setting the utility of such a center in our area, and the possible developing directions. It is our firm opinion that in case of failure to develop such a center, despite all the financial efforts directed toward the infrastructure of a modern Burn Unit affiliated to an University Accident Hospital, all the surgical experience cumulated during the past 13 years by a very motivated team, good quality results are still to be expected. Any patient with a deep second degree burn on more than 50% TBSA will be a potentially victim as in early 60s.

Trifluoromethyl-substituted polymers

NASA Technical Reports Server (NTRS)

1993-01-01

Current work sponsored by the grant at Southwest Texas State University is directed toward the synthesis and characterization of: (1) N-alkylated polyamides derived from o-fluorinated diacids; (2) highly fluorinated polyethers; (3) polyesters derived from 2-hydroxy-2-propyl substituted arenes and/or 2,5-difluoroterephthalic acid; and (4) silicon-containing fluoropolymers. Work during the period from 1 July to 31 Dec. 1993 focused primarily on items 3 and 4 and on the development of a phosphorus containing modification of '12F-PEK.'

Synthesis of 6-alkyluridines from 6-cyanouridine via zinc(II) chloride-catalyzed nucleophilic substitution with alkyl Grignard reagents.

PubMed

Shih, Yu-Chiao; Yang, Ya-Ying; Lin, Chun-Chi; Chien, Tun-Cheng

2013-04-19

6-Cyanouracil derivatives underwent a direct nucleophilic substitution reaction with alkyl Grignard reagents in the presence of zinc(II) chloride as a catalyst to form the corresponding 6-alkyluracils. This methodology is applicable to sugar-protected 6-cyanouridine and 6-cyano-2'-deoxyuridine without the protection at the N(3)-imide and provides a facile and general access to versatile 6-alkyluracil and 6-alkyluridine derivatives.

In vivo directed evolution for thermostabilization of Escherichia coli hygromycin B phosphotransferase and the use of the gene as a selection marker in the host-vector system of Thermus thermophilus.

PubMed

Nakamura, Akira; Takakura, Yasuaki; Kobayashi, Hideo; Hoshino, Takayuki

2005-08-01

An in vivo-directed evolutionary strategy was used to obtain a thermostabilized Escherichia coli hygromycin B phosphotransferase, using a host-vector system of Thermus thermophilus. Introduction of the mutant gene containing two amino acid substitutions, S52T and W238C, which was previously reported by Cannio et al. [J. Bacteriol., 180, 3237-3240 (1998)], did not confer hygromycin resistance on T. thermophilus cells at 55 degrees C; however, five spontaneously-generated independent mutants were obtained by selection of the transformants at this temperature. Each mutant gene contained one amino acid substitution of either A118V or T246A. Further selection with increasing temperature, at 58 degrees C and then 61 degrees C, led to acquisition of three more substitutions: D20G, S225P and Q226L. These mutations cumulatively influenced the maximum growth temperature of the T. thermophilus transformants in the presence of hygromycin; T. thermophilus carrying a mutant gene containing all the five substitutions was able to grow at up to 67 degrees C. This mutant gene, hph5, proved useful as a selection marker in the T. thermophilus host-vector system, either on the plasmid or by genome integration, at temperatures up to 65 degrees C.

Direct observation of the topological spin configurations mediated by the substitution of rare-earth element Y in MnNiGa alloy.

PubMed

Zuo, S L; Zhang, Y; Peng, L C; Zhao, X; Li, R; Li, H; Xiong, J F; He, M; Zhao, T Y; Sun, J R; Hu, F X; Shen, B G

2018-02-01

The evolution of topological magnetic domains microscopically correlates the dynamic behavior of memory units in spintronic application. Nanometric bubbles with variation of spin configurations have been directly observed in a centrosymmetric hexagonal magnet (Mn 0.5 Ni 0.5 ) 65 (Ga 1-y Y y ) 35 (y = 0.01) using Lorentz transmission electron microscopy. Magnetic bubbles instead of biskyrmions are generated due to the enhancement of quality factor Q caused by the substitution of rare-earth element Y. Furthermore, the bubble density and diversified spin configurations are systematically manipulated via combining the electric current with perpendicular magnetic fields. The magnetic bubble lattice at zero field is achieved after the optimized manipulation.

Structural and magnetic properties of Ni1-xZnxFe2O4 synthesized through the sol-gel method

NASA Astrophysics Data System (ADS)

Guan, Beh Hoe; Zahari, Muhammad Hanif; Chuan, Lee Kean

2016-11-01

Modification of crystal structure by means of substitution would result in the modification of the overall physical properties of crystallite materials especially in ferrites. This study aims to investigate the effect of non-magnetic Zn substitution in spinel NiFe2O4 and its direct effect towards its microstructural and magnetic properties. Magnetic nanoparticles of Nickel-Zinc ferrite with the chemical formula, Ni1-xZnxFe2O4 (x=0.00, 0.25, 0.50, 0.75) were synthesized through the sol-gel route. Phase formation and structural properties of the synthesized ferrite were identified through X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM). Magnetic properties such as the magnetic saturation, coercivity and remanence were measured by a vibrating sample magnetometer (VSM). XRD measurements reveals successful synthesis of single-phased Nickel ferrite and Nickel—Zinc ferrite. Both crystallite and grain size shows fluctuation with increasing Zn content. The ferrites were found to be ferrimagnetic in nature and show differing values with different x values.

Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

PubMed Central

Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

2016-01-01

Olefin metathesis has made a significant impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is very limited. In this manuscript, we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of an in situ-generated catalyst with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents and proceed to high conversion at ambient temperature within four hours. Many alkenyl chlorides, bromides and fluorides can be obtained in up to 91 percent yield and complete Z selectivity. This method can be used to easily synthesize biologically active compounds and to perform the site- and stereoselective fluorination of other organic compounds. PMID:27008965

Analysis of polycyclic aromatic hydrocarbons using desorption atmospheric pressure chemical ionization coupled to a portable mass spectrometer.

PubMed

Jjunju, Fred P M; Maher, Simon; Li, Anyin; Badu-Tawiah, Abraham K; Taylor, Stephen; Cooks, R Graham

2015-02-01

Desorption atmospheric pressure chemical ionization (DAPCI) is implemented on a portable mass spectrometer and applied to the direct detection of polycyclic aromatic hydrocarbons (PAHs) and alkyl substituted benzenes. The presence of these compounds in the environment poses a significant threat to the health of both humans and wildlife because of their carcinogenic, toxic, and mutagenic properties. As such, instant detection outside of the laboratory is of particular importance to allow in-situ measurement at the source. Using a rapid, high throughput, miniature, handheld mass spectrometer, several alkyl substituted benzenes and PAHs (i.e., 1,2,3,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, fluoranthene, anthracene, benzo[k]fluoranthene, dibenz[a,h]anthracene, acenaphthene, indeno[1,2,3-c,d]pyrene, 9-ethylfluorene, and 1-benzyl-3-methyl-naphthalene) were identified and characterized using tandem mass spectrometry (MS/MS) from ambient surfaces, in the open air. This method can provide almost instantaneous information while minimizing sample preparation, which is advantageous in terms of both cost and simplicity of analysis. This MS-based technique is applicable to a wide range of environmental organic molecules.

Probing the role of the vancomycin e-ring aryl chloride: selective divergent synthesis and evaluation of alternatively substituted E-ring analogues.

PubMed

Pinchman, Joseph R; Boger, Dale L

2013-05-23

The selective functionalization of vancomycin aglycon derivatives through conversion of the E-ring aryl chloride to a reactive boronic acid and its use in the synthesis of a systematic series of vancomycin E-ring analogues are described. The series was used to examine the E-ring chloride impact in binding d-Ala-d-Ala and on antimicrobial activity. In contrast to the reduced activity of the unsubstituted E-ring derivatives, hydrophobic and relatively nonpolar substituents approach or match the chloro-substituted vancomycin and were insensitive to the electronic character of the substituent (e.g., Cl vs CN/OMe), whereas highly polar substituents fail to provide the enhancements. Moreover, the active permethylated vancomycin aglycon derivatives exhibit VanB VRE antimicrobial activity at levels that approach (typically within 2-fold) their activity against sensitive bacteria. The robust borylation reaction also enabled the functionalization of a minimally protected vancomycin aglycon (N-Boc-vancomycin aglycon) and provides a direct method for the preparation of previously inaccessible analogues.

Models for the dynamics of dust-like matter in the self-gravity field: The method of hydrodynamic substitutions

NASA Astrophysics Data System (ADS)

Zhuravlev, V. M.

2017-09-01

Models for the dynamics of a dust-like medium in the self-gravity field are investigated. Solutions of the corresponding problems are constructed by the method of hydrodynamic substitutions generalizing the Cole-Hopf substitutions. The method is extended to multidimensional ideal and viscous fluid flows with cylindrical and spherical symmetries for which exact solutions are constructed. Solutions for the dynamics of self-gravitating dust with arbitrary initial distributions of both fluid density and velocity are constructed using special coordinate transformations. In particular, the problem of cosmological expansion is considered in terms of Newton's gravity theory. Models of a one-dimensional viscous dust fluid flow and some problems of gas hydrodynamics are considered. Examples of exact solutions and their brief analysis are provided.

Structure and magnetic properties of flux grown single crystals of Co3-xFexSn2S2 shandites

NASA Astrophysics Data System (ADS)

Kassem, Mohamed A.; Tabata, Yoshikazu; Waki, Takeshi; Nakamura, Hiroyuki

2016-01-01

We report a successful single crystal growth of the shandite-type half-metallic ferromagnet Co3Sn2S2, and its Fe-substituted compounds, Co3-xFexSn2S2, by employing the flux method. Although Fe3Sn2S2 is unstable phase, we found that using the self Sn flux enables us to obtain single phase crystals up to x=0.53. The chemical composition of the grown plate-shaped single crystals was examined using wavelength-dispersive X-ray spectroscopy. The shandite structure with R 3 ̅m symmetry was confirmed by powder X-ray diffraction and the crystal structure parameters were refined using the Rietveld method. Magnetization measurements show suppression of the ferromagnetic order upon Fe-substitution , as well as in other substituted systems such as In- and Ni-substituted Co3Sn2S2. The almost identical magnetic phase diagrams of the Fe- and In-substituted compounds indicate that the electron number is dominantly significant to the magnetism in the Co-based shandite.

Drastic effect of the Mn-substitution in the strongly correlated semiconductor FeSb2.

NASA Astrophysics Data System (ADS)

Kassem, Mohamed A.; Tabata, Yoshikazu; Waki, Takeshi; Nakamura, Hiroyuki

2017-06-01

We report the effects of Mn substitution, corresponding to hole doping, on the electronic properties of the narrow gap semiconductor, FeSb2, using single crystals of Fe1- x Mn x Sb2 grown by the Sb flux method. The orthorhombic Pnnm structure was confirmed by powder X-ray diffraction (XRD) for the pure and Mn-substituted samples. Their crystal structure parameters were refined using the Rietveld method. The chemical composition was investigated by wavelength-dispersive X-ray spectroscopy (WDX). The solubility limit of Mn in FeSb2 is x max ˜ 0.05 and the lattice constants change monotonically with increasing the actual Mn concentration. A drastic change from semiconducting to metallic electronic transports was found at very low Mn concentration at x ˜ 0.01. Our experimental results and analysis indicate that the substitution of a small amount of Mn changes drastically the electronic state in FeSb2 as well as the Co-substitution does: closing of the narrow gap and emergence of the density of states (DOS) at the Fermi level.

Anti-cancer agents based on N-acyl-2, 3-dihydro-1H-pyrrolo[2,3-b] quinoline derivatives and a method of making

DOEpatents

Gakh, Andrei; Krasavin, Mikhail; Karapetian, Ruben; Rufanov, Konstantin A; Konstantinov, Igor; Godovykh, Elena; Soldatkina, Olga; Sosnov, Andrey V

2013-04-16

The present disclosure relates to novel compounds that can be used as anti-cancer agents in the prostate cancer therapy. In particular, the invention relates to N-acyl derivatives of 2,3-dihydro-1H-pyrrolo[2,3-b]quinolines having the structural Formula (I), ##STR00001## stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof. The meaning of R1 is independently selected from H; C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl substituents; R2 is selected from C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl; substituted or non-substituted, fused or non-fused to substituted or non-substituted aromatic ring, aryl or heteroaryl groups. The invention also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

Directional Slack-Based Measure for the Inverse Data Envelopment Analysis

PubMed Central

Abu Bakar, Mohd Rizam; Lee, Lai Soon; Jaafar, Azmi B.; Heydar, Maryam

2014-01-01

A novel technique has been introduced in this research which lends its basis to the Directional Slack-Based Measure for the inverse Data Envelopment Analysis. In practice, the current research endeavors to elucidate the inverse directional slack-based measure model within a new production possibility set. On one occasion, there is a modification imposed on the output (input) quantities of an efficient decision making unit. In detail, the efficient decision making unit in this method was omitted from the present production possibility set but substituted by the considered efficient decision making unit while its input and output quantities were subsequently modified. The efficiency score of the entire DMUs will be retained in this approach. Also, there would be an improvement in the efficiency score. The proposed approach was investigated in this study with reference to a resource allocation problem. It is possible to simultaneously consider any upsurges (declines) of certain outputs associated with the efficient decision making unit. The significance of the represented model is accentuated by presenting numerical examples. PMID:24883350

Tactile pavement for guiding walking direction: An assessment of heading direction and gait stability.

PubMed

Pluijter, Nanda; de Wit, Lieke P W; Bruijn, Sjoerd M; Plaisier, Myrthe A

2015-10-01

For maintaining heading direction while walking we heavily rely on vision. Therefore, walking in the absence of vision or with visual attention directed elsewhere potentially leads to dangerous situations. Here we investigated whether tactile information from the feet can be used as a (partial) substitute for vision in maintaining a stable heading direction. If so, participants should be better able to keep a constant heading direction on tactile pavement that indicates directionality than on regular flat pavement. However, such a pavement may also be destabilizing. Thus we asked participants to walk straight ahead on regular pavement, and on tactile pavement (tiles with ridges along the walking direction) while varying the amount of vision. We assessed the effects of the type of pavement as well as the amount of vision on the variability of the heading direction as well as gait stability. Both of these measures were calculated from accelerations and angular velocities recorded from a smartphone attached to the participants trunk. Results showed that on tactile pavement participants had a less variations in their heading direction than on regular pavement. The drawback, however, was that the tactile pavement used in this study decreased gait stability. In sum, tactile pavement can be used as a partial substitute for vision in maintaining heading direction, but it can also decrease gait stability. Future work should focus on designing tactile pavement that does provided directional clues, but is less destabilizing. Copyright © 2015 Elsevier B.V. All rights reserved.

Rapid embedding methods into epoxy and LR White resins for morphological and immunological analysis of cryofixed biological specimens.

PubMed

McDonald, Kent L

2014-02-01

A variety of specimens including bacteria, ciliates, choanoflagellates (Salpingoeca rosetta), zebrafish (Danio rerio) embryos, nematode worms (Caenorhabditis elegans), and leaves of white clover (Trifolium repens) plants were high pressure frozen, freeze-substituted, infiltrated with either Epon, Epon-Araldite, or LR White resins, and polymerized. Total processing time from freezing to blocks ready to section was about 6 h. For epoxy embedding the specimens were freeze-substituted in 1% osmium tetroxide plus 0.1% uranyl acetate in acetone. For embedding in LR White the freeze-substitution medium was 0.2% uranyl acetate in acetone. Rapid infiltration was achieved by centrifugation through increasing concentrations of resin followed by polymerization at 100°C for 1.5-2 h. The preservation of ultrastructure was comparable to standard freeze substitution and resin embedding methods that take days to complete. On-section immunolabeling results for actin and tubulin molecules were positive with very low background labeling. The LR White methods offer a safer, quicker, and less-expensive alternative to Lowicryl embedding of specimens processed for on-section immunolabeling without traditional aldehyde fixatives.

Transient-state kinetic approach to mechanisms of enzymatic catalysis.

PubMed

Fisher, Harvey F

2005-03-01

Transient-state kinetics by its inherent nature can potentially provide more directly observed detailed resolution of discrete events in the mechanistic time courses of enzyme-catalyzed reactions than its more widely used steady-state counterpart. The use of the transient-state approach, however, has been severely limited by the lack of any theoretically sound and applicable basis of interpreting the virtual cornucopia of time and signal-dependent phenomena that it provides. This Account describes the basic kinetic behavior of the transient state, critically examines some currently used analytic methods, discusses the application of a new and more soundly based "resolved component transient-state time-course method" to the L-glutamate-dehydrogenase reaction, and establishes new approaches for the analysis of both single- and multiple-step substituted transient-state kinetic isotope effects.

Synthetic Bone Substitute Engineered with Amniotic Epithelial Cells Enhances Bone Regeneration after Maxillary Sinus Augmentation

PubMed Central

Barboni, Barbara; Mangano, Carlo; Valbonetti, Luca; Marruchella, Giuseppe; Berardinelli, Paolo; Martelli, Alessandra; Muttini, Aurelio; Mauro, Annunziata; Bedini, Rossella; Turriani, Maura; Pecci, Raffaella; Nardinocchi, Delia; Zizzari, Vincenzo Luca; Tetè, Stefano; Piattelli, Adriano; Mattioli, Mauro

2013-01-01

Background Evidence has been provided that a cell-based therapy combined with the use of bioactive materials may significantly improve bone regeneration prior to dental implant, although the identification of an ideal source of progenitor/stem cells remains to be determined. Aim In the present research, the bone regenerative property of an emerging source of progenitor cells, the amniotic epithelial cells (AEC), loaded on a calcium-phosphate synthetic bone substitute, made by direct rapid prototyping (rPT) technique, was evaluated in an animal study. Material And Methods Two blocks of synthetic bone substitute (∼0.14 cm3), alone or engineered with 1×106 ovine AEC (oAEC), were grafted bilaterally into maxillary sinuses of six adult sheep, an animal model chosen for its high translational value in dentistry. The sheep were then randomly divided into two groups and sacrificed at 45 and 90 days post implantation (p.i.). Tissue regeneration was evaluated in the sinus explants by micro-computer tomography (micro-CT), morphological, morphometric and biochemical analyses. Results And Conclusions The obtained data suggest that scaffold integration and bone deposition are positively influenced by allotransplantated oAEC. Sinus explants derived from sheep grafted with oAEC engineered scaffolds displayed a reduced fibrotic reaction, a limited inflammatory response and an accelerated process of angiogenesis. In addition, the presence of oAEC significantly stimulated osteogenesis either by enhancing bone deposition or making more extent the foci of bone nucleation. Besides the modulatory role played by oAEC in the crucial events successfully guiding tissue regeneration (angiogenesis, vascular endothelial growth factor expression and inflammation), data provided herein show that oAEC were also able to directly participate in the process of bone deposition, as suggested by the presence of oAEC entrapped within the newly deposited osteoid matrix and by their ability to switch-on the expression of a specific bone-related protein (osteocalcin, OCN) when transplanted into host tissues. PMID:23696804

Effect of Locked-Nucleic Acid on a Biologically Active G-Quadruplex. A Structure-Activity Relationship of the Thrombin Aptamer

PubMed Central

Bonifacio, Laura; Church, Frank C.; Jarstfer, Michael B.

2008-01-01

Here we tested the ability to augment the biological activity of the thrombin aptamer, d(GGTTGGTGTGGTTGG), by using locked nucleic acid (LNA) to influence its G-quadruplex structure. Compared to un-substituted control aptamer, LNA-containing aptamers displayed varying degrees of thrombin inhibition. Aptamers with LNA substituted in either positions G5, T7, or G8 showed decreased thrombin inhibition, whereas LNA at position G2 displayed activity comparable to un-substituted control aptamer. Interestingly, the thermal stability of the substituted aptamers does not correlate to activity – the more stable aptamers with LNA in position G5, T7, or G8 showed the least thrombin inhibition, while a less stable aptamer with LNA at G2 was as active as the un-substituted aptamer. These results suggest that LNA substitution at sites G5, T7, and G8 directly perturbs aptamer-thrombin affinity. This further implies that for the thrombin aptamer, activity is not dictated solely by the stability of the G-quadruplex structure, but by specific interactions between the central TGT loop and thrombin and that LNA can be tolerated in a biologically active nucleic acid structure albeit in a position dependent fashion. PMID:19325759

Identification of single amino acid substitutions (SAAS) in neuraminidase from influenza a virus (H1N1) via mass spectrometry analysis coupled with de novo peptide sequencing.

PubMed

Peng, Qisheng; Wang, Zijian; Wu, Donglin; Li, Xiaoou; Liu, Xiaofeng; Sun, Wanchun; Liu, Ning

2016-08-01

Amino acid substitutions in the neuraminidase of the influenza virus are the main cause of the emergence of resistance to zanamivir or oseltamivir during seasonal influenza treatment; they are the result of non-synonymous mutations in the viral genome that can be successfully detected by polymer chain reaction (PCR)-based approaches. There is always an urgent need to detect variation in amino acid sequences directly at the protein level. Mass spectrometry coupled with de novo sequencing has been explored as an alternative and straightforward strategy for detecting amino acid substitutions, as well - this approach is the primary focus of the present study. Influenza virus (A/Puerto Rico/8/1934 H1N1) propagated in embryonated chicken eggs was purified by ultracentrifugation, followed by PNGase F treatment. The deglycosylated virion was lysed and separated by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The gel band corresponding to neuraminidase was picked up and subjected to liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. LC-MS/MS analyses, coupled with manual de novo sequencing, allowed the determination of three amino acid substitutions: R346K, S349 N, and S370I/L, in the neuraminidase from the influenza virus (A/Puerto Rico/8/1934 H1N1), which were located in three mutated peptides of the neuraminidase: YGNGVWIGK, TKNHSSR, and PNGWTETDI/LK, respectively. We found that the amino acid substitutions in the proteins of RNA viruses (including influenza A virus) resulting from non-synonymous gene mutations can indeed be directly analyzed via mass spectrometry, and that manual interpretation of the MS/MS data may be beneficial. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Recycling of plastic: accounting of greenhouse gases and global warming contributions.

PubMed

Astrup, Thomas; Fruergaard, Thilde; Christensen, Thomas H

2009-11-01

Major greenhouse gas (GHG) emissions related to plastic waste recycling were evaluated with respect to three management alternatives: recycling of clean, single-type plastic, recycling of mixed/contaminated plastic, and use of plastic waste as fuel in industrial processes. Source-separated plastic waste was received at a material recovery facility (MRF) and processed for granulation and subsequent downstream use. In the three alternatives, plastic was assumed to be substituting virgin plastic in new products, wood in low-strength products (outdoor furniture, fences, etc.), and coal or fuel oil in the case of energy utilization. GHG accounting was organized in terms of indirect upstream emissions (e.g. provision of energy, fuels, and materials), direct emissions at the MRF (e.g. fuel combustion), and indirect downstream emissions (e.g. avoided emissions from production of virgin plastic, wood, or coal/oil). Combined, upstream and direct emissions were estimated to be roughly between 5 and 600 kg CO(2)-eq. tonne( -1) of plastic waste depending on treatment at the MRF and CO(2) emissions from electricity production. Potential downstream savings arising from substitution of virgin plastic, wood, and energy fuels were estimated to be around 60- 1600 kg CO(2)-eq. tonne( -1) of plastic waste depending on substitution ratios and CO(2) emissions from electricity production. Based on the reviewed data, it was concluded that substitution of virgin plastic should be preferred. If this is not viable due to a mixture of different plastic types and/or contamination, the plastic should be used for energy utilization. Recycling of plastic waste for substitution of other materials such as wood provided no savings with respect to global warming.

Incorporating Alternative Care Site Characteristics Into Estimates of Substitutable ED Visits.

PubMed

Trueger, Nathan Seth; Chua, Kao-Ping; Hussain, Aamir; Liferidge, Aisha T; Pitts, Stephen R; Pines, Jesse M

2017-07-01

Several recent efforts to improve health care value have focused on reducing emergency department (ED) visits that potentially could be treated in alternative care sites (ie, primary care offices, retail clinics, and urgent care centers). Estimates of the number of these visits may depend on assumptions regarding the operating hours and functional capabilities of alternative care sites. However, methods to account for the variability in these characteristics have not been developed. To develop methods to incorporate the variability in alternative care site characteristics into estimates of ED visit "substitutability." Our approach uses the range of hours and capabilities among alternative care sites to estimate lower and upper bounds of ED visit substitutability. We constructed "basic" and "extended" criteria that captured the plausible degree of variation in each site's hours and capabilities. To illustrate our approach, we analyzed data from 22,697 ED visits by adults in the 2011 National Hospital Ambulatory Medical Care Survey, defining a visit as substitutable if it was treat-and-release and met both the operating hours and functional capabilities criteria. Use of the combined basic hours/basic capabilities criteria and extended hours/extended capabilities generated lower and upper bounds of estimates. Our criteria classified 5.5%-27.1%, 7.6%-20.4%, and 10.6%-46.0% of visits as substitutable in primary care offices, retail clinics, and urgent care centers, respectively. Alternative care sites vary widely in operating hours and functional capabilities. Methods such as ours may help incorporate this variability into estimates of ED visit substitutability.

Suicide by Jumping and Accessibility of Bridges: Results from a National Survey in Switzerland

ERIC Educational Resources Information Center

Reisch, Thomas; Schuster, Ursula; Michel, Konrad

2007-01-01

Rates of suicide by jumping show large regional differences. Barriers on bridges may prevent suicides but also may lead to a substitution of jumping site or method. The aim of our study was to compare suicide data from regions with and without suicide bridges and to estimate the effects on method and site substitution if bridges were to be…

Opting Out and Buying Out: Wives’ Earnings and Housework Time

PubMed Central

Killewald, Alexandra

2011-01-01

It has been proposed that the negative association between wives’ earnings and their time in housework is due to greater outsourcing of household labor by households with high-earning wives, but this hypothesis has not been tested directly. In a sample of dual-earner married couples in the Consumption and Activities Mail Survey of the Health and Retirement Study (N = 796), use of market substitutes for women’s housework was found to be only weakly associated with wives’ time cooking and cleaning. Furthermore, expenditures on market substitutes explain less than 15% of the earnings–housework time relationship. This suggests that use of market substitutes plays a smaller role in explaining variation in wives’ time in household labor than has previously been hypothesized. PMID:22053115

The long-sought seventeen-electron radical [(C6Me6)Cr(CO)3](+): isolation, crystal structure and substitution reaction.

PubMed

Wang, Wenqing; Wang, Xingyong; Zhang, Zaichao; Yuan, Ningning; Wang, Xinping

2015-05-18

A highly air-sensitive seventeen-electron half-sandwich radical, [(C6Me6)Cr(CO)3](+), which has been long sought over 40 years, was isolated and structurally characterized. EPR spectroscopy and theoretical calculations indicate that the spin density mainly resides on the chromium atom. The radical can undergo a substitution reaction with PPh3 to form a more stable cation, [(C6Me6)Cr(CO)2(PPh3)](+). This work provides a direct observation of the radical process for CO-substitution reactions found in (arene)M(CO)3 (M = Cr, Mo, or W) systems, and suggests that other stable radicals of the type [(arene)M(CO)3](+) are accessible.

Surface Engineering and Patterning Using Parylene for Biological Applications

PubMed Central

Tan, Christine P.; Craighead, Harold G.

2010-01-01

Parylene is a family of chemically vapour deposited polymer with material properties that are attractive for biomedicine and nanobiotechnology. Chemically inert parylene “peel-off” stencils have been demonstrated for micropatterning biomolecular arrays with high uniformity, precise spatial control down to nanoscale resolution. Such micropatterned surfaces are beneficial in engineering biosensors and biological microenvironments. A variety of substituted precursors enables direct coating of functionalised parylenes onto biomedical implants and microfluidics, providing a convenient method for designing biocompatible and bioactive surfaces. This article will review the emerging role and applications of parylene as a biomaterial for surface chemical modification and provide a future outlook.

Frontier production function estimates for steam electric generation: a comparative analysis

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

Kopp, R.J.; Smith, V.K.

1980-04-01

The performance of three frontier steam electric generation estimators is compared in terms of the consideration given to new production technologies and their technical efficiency. The Cobb-Douglas, constant elasticity of substitution, and translog production functions are examined, using the Aigner-Chu linear programming, the sophisticated Aigner-Lovell-Schmidt stochastic frontier, and the direct method of adjusted ordinary least squares frontier estimators. The use of Cobb-Douglas specification is judged to have narrowed the perceived difference between competing estimators. The choice of frontier estimator is concluded to have a greater effect on the plant efficiency than functional form. 19 references. (DCK)

Determination of active oxygen in the presence of barium and lead

USGS Publications Warehouse

Fleischer, M.

1943-01-01

The method of Mrgudich and Clark is modified by substituting 5 per cent (by volume) perchloric acid for 50 per cent perchloric acid. Titration by potassium permanganate may be substituted for electrometric titration with ceric sulfate.

Regression and direct methods do not give different estimates of digestible and metabolizable energy values of barley, sorghum, and wheat for pigs.

PubMed

Bolarinwa, O A; Adeola, O

2016-02-01

Direct or indirect methods can be used to determine the DE and ME of feed ingredients for pigs. In situations when only the indirect approach is suitable, the regression method presents a robust indirect approach. Three experiments were conducted to compare the direct and regression methods for determining the DE and ME values of barley, sorghum, and wheat for pigs. In each experiment, 24 barrows with an average initial BW of 31, 32, and 33 kg were assigned to 4 diets in a randomized complete block design. The 4 diets consisted of 969 g barley, sorghum, or wheat/kg plus minerals and vitamins for the direct method; a corn-soybean meal reference diet (RD); the RD + 300 g barley, sorghum, or wheat/kg; and the RD + 600 g barley, sorghum, or wheat/kg. The 3 corn-soybean meal diets were used for the regression method. Each diet was fed to 6 barrows in individual metabolism crates for a 5-d acclimation followed by a 5-d period of total but separate collection of feces and urine in each experiment. Graded substitution of barley or wheat, but not sorghum, into the RD linearly reduced ( < 0.05) dietary DE and ME. The direct method-derived DE and ME for barley were 3,669 and 3,593 kcal/kg DM, respectively. The regressions of barley contribution to DE and ME in kilocalories against the quantity of barley DMI in kilograms generated 3,746 kcal DE/kg DM and 3,647 kcal ME/kg DM. The DE and ME for sorghum by the direct method were 4,097 and 4,042 kcal/kg DM, respectively; the corresponding regression-derived estimates were 4,145 and 4,066 kcal/kg DM. Using the direct method, energy values for wheat were 3,953 kcal DE/kg DM and 3,889 kcal ME/kg DM. The regressions of wheat contribution to DE and ME in kilocalories against the quantity of wheat DMI in kilograms generated 3,960 kcal DE/kg DM and 3,874 kcal ME/kg DM. The DE and ME of barley using the direct method were not different (0.3 < < 0.4) from those obtained using the regression method (3,669 vs. 3,746 and 3,593 vs. 3,647 kcal/kg DM, respectively). The direct method-derived DE and ME of sorghum were not different (0.5 < < 0.7) from those obtained using the regression method (4,097 vs. 4,145 and 4,042 vs. 4,066 kcal/kg DM, respectively). The direct method- and regression method-derived DE (3,953 and 3,960 kcal/kg DM, respectively) and ME (3,889 and 3,874 kcal/kg DM, respectively) of wheat were not different (0.8 < < 0.9). Results of these 3 experiments suggest that regression and direct methods do not give different estimates of DE and ME in barley, sorghum, and wheat for pigs.

GNSS Single Frequency, Single Epoch Reliable Attitude Determination Method with Baseline Vector Constraint.

PubMed

Gong, Ang; Zhao, Xiubin; Pang, Chunlei; Duan, Rong; Wang, Yong

2015-12-02

For Global Navigation Satellite System (GNSS) single frequency, single epoch attitude determination, this paper proposes a new reliable method with baseline vector constraint. First, prior knowledge of baseline length, heading, and pitch obtained from other navigation equipment or sensors are used to reconstruct objective function rigorously. Then, searching strategy is improved. It substitutes gradually Enlarged ellipsoidal search space for non-ellipsoidal search space to ensure correct ambiguity candidates are within it and make the searching process directly be carried out by least squares ambiguity decorrelation algorithm (LAMBDA) method. For all vector candidates, some ones are further eliminated by derived approximate inequality, which accelerates the searching process. Experimental results show that compared to traditional method with only baseline length constraint, this new method can utilize a priori baseline three-dimensional knowledge to fix ambiguity reliably and achieve a high success rate. Experimental tests also verify it is not very sensitive to baseline vector error and can perform robustly when angular error is not great.

A Constant Pressure Bomb

NASA Technical Reports Server (NTRS)

Stevens, F W

1924-01-01

This report describes a new optical method of unusual simplicity and of good accuracy suitable to study the kinetics of gaseous reactions. The device is the complement of the spherical bomb of constant volume, and extends the applicability of the relationship, pv=rt for gaseous equilibrium conditions, to the use of both factors p and v. The method substitutes for the mechanical complications of a manometer placed at some distance from the seat of reaction the possibility of allowing the radiant effects of reaction to record themselves directly upon a sensitive film. It is possible the device may be of use in the study of the photoelectric effects of radiation. The method makes possible a greater precision in the measurement of normal flame velocities than was previously possible. An approximate analysis shows that the increase of pressure and density ahead of the flame is negligible until the velocity of the flame approaches that of sound.

Polybenzimidazole compounds

DOEpatents

Klaehn, John R.; Peterson, Eric S.; Wertsching, Alan K.; Orme, Christopher J.; Luther, Thomas A.; Jones, Michael G.

2010-08-10

A PBI compound that includes imidazole nitrogens, at least a portion of which are substituted with an organic-inorganic hybrid moiety. At least 85% of the imidazole nitrogens may be substituted. The organic-inorganic hybrid moiety may be an organosilane moiety, for example, (R)Me.sub.2SiCH.sub.2--, where R is selected from among methyl, phenyl, vinyl, and allyl. The PBI compound may exhibit similar thermal properties in comparison to the unsubstituted PBI. The PBI compound may exhibit a solubility in an organic solvent greater than the solubility of the unsubstituted PBI. The PBI compound may be included in separatory media. A substituted PBI synthesis method may include providing a parent PBI in a less than 5 wt % solvent solution. Substituting may occur at about room temperature and/or at about atmospheric pressure. Substituting may use at least five equivalents in relation to the imidazole nitrogens to be substituted or, preferably, about fifteen equivalents.

Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

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

Mohebbi, Sajjad, E-mail: smohebbi@uok.ac.ir; Eslami, Saadat

2015-06-15

Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N{sub 2}O{sub 2} Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT andmore » new N{sub 2}O{sub 2} unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO{sub 2} and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity.« less

Adaptation of H9N2 AIV in guinea pigs enables efficient transmission by direct contact and inefficient transmission by respiratory droplets

PubMed Central

Sang, Xiaoyu; Wang, Airong; Ding, Jie; Kong, Huihui; Gao, Xiaolong; Li, Lin; Chai, Tongjie; Li, Yuanguo; Zhang, Kun; Wang, Chengyu; Wan, Zhonghai; Huang, Geng; Wang, Tiecheng; Feng, Na; Zheng, Xuexing; Wang, Hualei; Zhao, Yongkun; Yang, Songtao; Qian, Jun; Hu, Guixue; Gao, Yuwei; Xia, Xianzhu

2015-01-01

H9N2 avian influenza viruses circulate worldwide in poultry and have sporadically infected humans, raising concern whether H9N2 viruses have pandemic potential. Here, we use a guinea pig model to examine whether serial passage results in adaptive viral changes that confer a transmissible phenotype to a wild-type H9N2 virus. After nine serial passages of an H9N2 virus through guinea pigs, productive transmission by direct contact occurred in 2/3 guinea pig pairs. The efficiency of transmission by direct contact increased following the fifteenth passage and occurred in 3/3 guinea pig pairs. In contrast, airborne transmission of the passaged virus was less efficient and occurred in 1/6 guinea pig pairs and 0/6 ferret pairs after the fifteenth passage. Three amino acid substitutions, HA1-Q227P, HA2-D46E, and NP-E434K, were sufficient for contact transmission in guinea pigs (2/3 pairs). The two HA amino acid substitutions enhanced receptor binding to α2,3-linked sialic acid receptors. Additionally, the HA2-D46E substitution increased virus thermostability whereas the NP-E434K mutation enhanced viral RNA polymerase activity in vitro. Our findings suggest that adaptive changes that enhance viral receptor binding, thermostability, and replicative capacity in mammalian cells can collectively enhance the transmissibility of H9N2 AIVs by direct contact in the guinea pig model. PMID:26552719

Changes in Ultrasonic Velocity from Fluid Substitution, Calculated with Laboratory Methods, Digital Rock Physics, and Biot Theory

NASA Astrophysics Data System (ADS)

Goldfarb, E. J.; Ikeda, K.; Tisato, N.

2017-12-01

Seismic and ultrasonic velocities of rocks are function of several variables including fluid saturation and type. Understanding the effect of each variable on elastic waves can be valuable when using seismic methods for subsurface modeling. Fluid type and saturation are of specific interest to volcanology, water, and hydrocarbon exploration. Laboratory testing is often employed to understand the effects of fluids on elastic waves. However, laboratory testing is expensive and time consuming. It normally requires cutting rare samples into regular shapes. Fluid injection can also destroy specimens as removing the fluid after testing can prove difficult. Another option is theoretical modeling, which can be used to predict the effect of fluids on elastic properties, but it is often inaccurate. Alternatively, digital rock physics (DRP) can be used to investigate the effect of fluid substitution. DRP has the benefit of being non invasive, as it does not require regular sample shapes or fluid injection. Here, we compare the three methods for dry and saturated Berea sandstone to test the reliability of DRP. First, ultrasonic velocities were obtained from laboratory testing. Second, for comparison, we used a purely theoretical approach - i.e., Hashin-Shtrikman and Biot theory - to estimate the wave speeds at dry and wet conditions. Third, we used DRP. The dry sample was scanned with micro Computed Tomography (µCT), and a three dimensional (3D) array was recorded. We employed a segmentation-less method to convert each 3D array value to density, porosity, elastic moduli, and wave speeds. Wave propagation was simulated numerically at similar frequency as the laboratory. To simulate fluid substitution, we numerically substituted air values for water and repeated the simulation. The results from DRP yielded similar velocities to the laboratory, and accurately predicted the velocity change from fluid substitution. Theoretical modeling could not accurately predict velocity, and under-predicted the velocity change from fluid substitution. The mathematical approach proved to be a poor comparison for the laboratory measurement. DRP proved to be effective, and could be used in future with drill cuttings, perhaps to limit the use of expensive cores. DRP could also limit the requirement for physically testing fluid substitution.

Solution combustion method for synthesis of nanostructured hydroxyapatite, fluorapatite and chlorapatite

NASA Astrophysics Data System (ADS)

Zhao, Junjie; Dong, Xiaochen; Bian, Mengmeng; Zhao, Junfeng; Zhang, Yao; Sun, Yue; Chen, JianHua; Wang, XuHong

2014-09-01

Hydroxyapatite (HAP), fluorapatite (Fap) and chlorapatite (Clap) were prepared by solution combustion method with further annealing at 800 °C. The characterization and structural features of the synthesized powders were evaluated by the powder X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques. Characterization results from XRD and Rietveld analysis revealed that OH- in the HAP lattice were gradually substituted with the increase of F- and Cl- content and totally substituted at the molar concentration of 0.28 and 0.6, respectively. The results from FI-IR have also confirmed the incorporation of substituted anions in the apatite structure.

Synthesis and Characterization of Novel Transition Metal Chalcogenide Phases for Energy Storage, Energy Conversion and Optoelectronics

NASA Astrophysics Data System (ADS)

Chen, Erica Maxine

Today's energy needs are primarily provided by fossil fuels, which are harvested from the earth. Consuming fossil fuels to provide energy for civilization releases products into the atmosphere that contribute to climate change. Ongoing efforts to combat the existential crisis which climate change presents many of the emerging and commercialized technologies for solar, thermoelectric and battery applications involve transition metal chalcogenides. Some of the materials used for these applications are expensive and rare, such as gallium, vanadium and indium, or have no merits towards environmental stewardship, such as cadmium and lead. Thus, the purpose of this work is to further the ongoing effort to discover and develop new materials which are able to meet or exceed benchmarks for their application. This work focuses on the development of various metal chalcogenide material systems featuring d-block transition metals selected for their contribution to alter structure and properties. Various thermal, electronic and optical properties can be changed through substitution or doping with additional elements to affect to the base composition or as part of a gradient composition series. After an extensive description of experimental methods which describe the associated materials synthesis, processing and characterization techniques in chapter 2, chapter 3 explores the Cu4-xLixS 2 phases for their contribution as further evidence in the formation of lithiated copper sulfide phases as part of the intercalation reaction before being converted to the binaries copper and lithium sulfide. Chapter 4 documents the development of Cu4TiSe4, a novel material with potential for thin-film photovoltaic technologies with its band gap in the range where the solar spectrum is the most bountiful (Eg,indirect = 1.16 eV, Eg,direct = 1.34 eV), an outstanding optical absorbance ( > 10-4 cm-1) outperforming commercially successful materials in the solar spectrum, and suitable for thin-film fabrication. Chapter 5 describes a brief study in utilizing elemental substitution in Cu4TiSe4 to alter the band gap by replacing sulfur into the selenium site. In this study, the amount of selenium which may be substituted without deviating from the parent Cu4TiSe4 structure is 16 % at and the direct band gap is alterable from 1.34 eV to 1.64 eV as determined from conducting tauc analysis on the diffuse reflectance spectra. The last experimental work in Chapter 6 covers the development of a chemical substitution series between the end compounds Cu3NbS 4 and Cu3NbSe4. Through powdered x-ray diffraction of the series, it was found that for substituting less than 25% of the sulfur with selenium, the powdered patterns more closely resembled Cu3NbS 4 and with shift which may see further development and application in optoelectronic devices such as LEDs. Finally, Chapter 7 provides further guidance in the research which this thesis may serve as a springboard for the development of ultra-high efficiency, low-cost, environmentally friendly and thin photovoltaics as well as mention other characterization methods which are necessary to diagnose and elucidate complications.

Magnetic moment directions and distributions of cations in Cr (Co) substituted spinel ferrites Ni{sub 0.7}Fe{sub 2.3}O{sub 4}

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

Xue, L. C.; Lang, L. L.; Li, Z. Z.

2015-09-15

Powder samples of the spinel ferrites M{sub x}Ni{sub 0.7−x}Fe{sub 2.3}O{sub 4} (M = Cr, Co and 0.0 ≤ x ≤ 0.3) and Cr{sub x}Ni{sub 0.7}Fe{sub 2.3−x}O{sub 4} (0.0 ≤ x ≤ 0.3) were synthesized using the chemical co-precipitation method. The XRD spectra confirmed that the samples had a single-phase cubic spinel structure. Magnetic measurements showed that the magnetic moments (μ{sub exp}) per formula both at 10 K and 300 K increased with Co substitution, while the values of μ{sub exp} decreased with Cr substitution. Applying the assumption that the magnetic moments of Cr{sup 2+} and Cr{sup 3+} lie antiparallel tomore » those of the divalent and trivalent Fe, Co, and Ni cations in the same sublattice of spinel ferrites, these interesting behaviors could be easily interpreted. The cation distributions of the three series of samples were estimated successfully by fitting the dependences of μ{sub exp}, measured at 10 K, on the doping level x, using a quantum-mechanical potential barrier model earlier proposed by our group. The results obtained for the Cr cation distributions at the (A) and [B] sites are very close to those obtained elsewhere using neutron diffraction.« less

Identification of Low- and High-Impact Hemagglutinin Amino Acid Substitutions That Drive Antigenic Drift of Influenza A(H1N1) Viruses

PubMed Central

Harvey, William T.; Benton, Donald J.; Gregory, Victoria; Hall, James P. J.; Daniels, Rodney S.; Bedford, Trevor; Haydon, Daniel T.; Hay, Alan J.; McCauley, John W.; Reeve, Richard

2016-01-01

Determining phenotype from genetic data is a fundamental challenge. Identification of emerging antigenic variants among circulating influenza viruses is critical to the vaccine virus selection process, with vaccine effectiveness maximized when constituents are antigenically similar to circulating viruses. Hemagglutination inhibition (HI) assay data are commonly used to assess influenza antigenicity. Here, sequence and 3-D structural information of hemagglutinin (HA) glycoproteins were analyzed together with corresponding HI assay data for former seasonal influenza A(H1N1) virus isolates (1997–2009) and reference viruses. The models developed identify and quantify the impact of eighteen amino acid substitutions on the antigenicity of HA, two of which were responsible for major transitions in antigenic phenotype. We used reverse genetics to demonstrate the causal effect on antigenicity for a subset of these substitutions. Information on the impact of substitutions allowed us to predict antigenic phenotypes of emerging viruses directly from HA gene sequence data and accuracy was doubled by including all substitutions causing antigenic changes over a model incorporating only the substitutions with the largest impact. The ability to quantify the phenotypic impact of specific amino acid substitutions should help refine emerging techniques that predict the evolution of virus populations from one year to the next, leading to stronger theoretical foundations for selection of candidate vaccine viruses. These techniques have great potential to be extended to other antigenically variable pathogens. PMID:27057693

Development and validation of a matrix solid-phase dispersion method to determine acrylamide in coffee and coffee substitutes.

PubMed

Soares, Cristina M Dias; Alves, Rita C; Casal, Susana; Oliveira, M Beatriz P P; Fernandes, José Oliveira

2010-04-01

The present study describes the development and validation of a new method based on a matrix solid-phase dispersion (MSPD) sample preparation procedure followed by GC-MS for determination of acrylamide levels in coffee (ground coffee and brewed coffee) and coffee substitute samples. Samples were dispersed in C(18) sorbent and the mixture was further packed into a preconditioned custom-made ISOLUTE bilayered SPE column (C(18)/Multimode; 1 g + 1 g). Acrylamide was subsequently eluted with water, and then derivatized with bromine and quantified by GC-MS in SIM mode. The MSPD/GC-MS method presented a LOD of 5 microg/kg and a LOQ of 10 microg/kg. Intra and interday precisions ranged from 2% to 4% and 4% to 10%, respectively. To evaluate the performance of the method, 11 samples of ground and brewed coffee and coffee substitutes were simultaneously analyzed by the developed method and also by a previously validated method based in a liquid-extraction (LE) procedure, and the results were compared showing a high correlation between them.

Rod Electroretinograms Elicited by Silent Substitution Stimuli from the Light-Adapted Human Eye

PubMed Central

Maguire, John; Parry, Neil R. A.; Kremers, Jan; Kommanapalli, Deepika; Murray, Ian J.; McKeefry, Declan J.

2016-01-01

Purpose To demonstrate that silent substitution stimuli can be used to generate electroretinograms (ERGs) that effectively isolate rod photoreceptor function in humans without the need for dark adaptation, and that this approach constitutes a viable alternative to current clinical standard testing protocols. Methods Rod-isolating and non-isolating sinusoidal flicker stimuli were generated on a 4 primary light-emitting diode (LED) Ganzfeld stimulator to elicit ERGs from participants with normal and compromised rod function who had not undergone dark-adaptation. Responses were subjected to Fourier analysis, and the amplitude and phase of the fundamental were used to examine temporal frequency and retinal illuminance response characteristics. Results Electroretinograms elicited by rod-isolating silent substitution stimuli exhibit low-pass temporal frequency response characteristics with an upper response limit of 30 Hz. Responses are optimal between 5 and 8 Hz and between 10 and 100 photopic trolands (Td). There is a significant correlation between the response amplitudes obtained with the silent substitution method and current standard clinical protocols. Analysis of signal-to-noise ratios reveals significant differences between subjects with normal and compromised rod function. Conclusions Silent substitution provides an effective method for the isolation of human rod photoreceptor function in subjects with normal as well as compromised rod function when stimuli are used within appropriate parameter ranges. Translational Relevance This method of generating rod-mediated ERGs can be achieved without time-consuming periods of dark adaptation, provides improved isolation of rod- from cone-based activity, and will lead to the development of faster clinical electrophysiologic testing protocols with improved selectivity. PMID:27617180

Fabrication of porous low crystalline calcite block by carbonation of calcium hydroxide compact.

PubMed

Matsuya, Shigeki; Lin, Xin; Udoh, Koh-ichi; Nakagawa, Masaharu; Shimogoryo, Ryoji; Terada, Yoshihiro; Ishikawa, Kunio

2007-07-01

Calcium carbonate (CaCO(3)) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO(3) monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO(3) monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO(2) through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8-48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.

Detecting Single-Nucleotide Substitutions Induced by Genome Editing.

PubMed

Miyaoka, Yuichiro; Chan, Amanda H; Conklin, Bruce R

2016-08-01

The detection of genome editing is critical in evaluating genome-editing tools or conditions, but it is not an easy task to detect genome-editing events-especially single-nucleotide substitutions-without a surrogate marker. Here we introduce a procedure that significantly contributes to the advancement of genome-editing technologies. It uses droplet digital polymerase chain reaction (ddPCR) and allele-specific hydrolysis probes to detect single-nucleotide substitutions generated by genome editing (via homology-directed repair, or HDR). HDR events that introduce substitutions using donor DNA are generally infrequent, even with genome-editing tools, and the outcome is only one base pair difference in 3 billion base pairs of the human genome. This task is particularly difficult in induced pluripotent stem (iPS) cells, in which editing events can be very rare. Therefore, the technological advances described here have implications for therapeutic genome editing and experimental approaches to disease modeling with iPS cells. © 2016 Cold Spring Harbor Laboratory Press.

Toluene nitration in irradiated nitric acid and nitrite solutions

NASA Astrophysics Data System (ADS)

Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.

2011-04-01

The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the rad NO2 radical.

Alkaline earth metallocenes coordinated with ester pendants: synthesis, structural characterization, and application in metathesis reactions.

PubMed

Li, Heng; Zhang, Wen-Xiong; Xi, Zhenfeng

2013-09-16

A variety of ester-substituted cyclopentadiene derivatives have been synthesized by one-pot reactions of 1,4-dilithio-1,3-butadienes, CO, and acid chlorides. Direct deprotonation of the ester-substituted cyclopentadienes with Ae[N(SiMe3 )2 ]2 (Ae=Ca, Sr, Ba) efficiently generated members of a new class of heavier alkaline earth (Ca, Sr, Ba) metallocenes in good to excellent yields. Single-crystal X-ray structural analysis demonstrated that these heavier alkaline earth metallocenes incorporated two intramolecularly coordinated ester pendants and multiply-substituted cyclopentadienyl ligands. The corresponding transition metal metallocenes, such as ferrocene derivatives and half-sandwich cyclopentadienyl tricarbonylrhenium complexes, could be generated highly efficiently by metathesis reactions. The multiply-substituted cyclopentadiene ligands bearing an ester pendant, and the corresponding heavier alkaline earth and transition-metal metallocenes, may have further applications in coordination chemistry, organometallic chemistry, and organic synthesis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Natural derivatives of diphenolic acid as substitutes for bisphenol-A

NASA Astrophysics Data System (ADS)

Ertl, Johanna; Cerri, Elisa; Rizzuto, Matteo; Caretti, Daniele

2014-05-01

Diphenolic acid had been originally used in the first epoxy resins and was later on forgotten as it was substituted by the cheaper bisphenol A. But in the recent years major health concerns have been raised as bisphenol A has a pseudo-hormonal effect on the body, playing the role of estrogen it can cause a severe impact on the organism, especially in males. Moreover it is produced from acetone and phenol, both from fossil, and thus limited resources. On the contrary, diphenolic acid is synthesized from levulinic acid and phenol. Levulinic acid being directly produced by hydrolysis of biomass. By substituting the fossil phenol with natural phenols from lignin or plant extraction we are able to synthesize a fully renewable substitute for bisphenol A. The reactions to yield an epoxy resin have been examined and the reactivity with epichlorohydrin is satisfying. Moreover, some of the derivatives of diphenolic acid have interesting curing properties and preliminary results show excellent properties of the cured resin, including thermal stability and pencil hardness.

Effectiveness of antimicrobial food packaging materials.

PubMed

Cooksey, K

2005-10-01

Antimicrobial additives have been used successfully for many years as direct food additives. The literature provides evidence that some of these additives may be effective as indirect food additives incorporated into food packaging materials. Antimicrobial food packaging is directed toward the reduction of surface contamination of processed, prepared foods such as sliced meats and Frankfurter sausages (hot dogs). The use of such packaging materials is not meant to be a substitute for good sanitation practices, but it should enhance the safety of food as an additional hurdle for the growth of pathogenic and/or spoilage microorganisms. Studies have focused on establishing methods for coating low-density polyethylene film or barrier films with methyl cellulose as a carrier for nisin. These films have significantly reduced the presence of Listeria monocytogenes in solutions and in vacuum packaged hot dogs. Other research has focused on the use of chitosan to inhibit L. monocytogenes and chlorine dioxide sachets for the reduction of Salmonella on modified atmosphere-packaged fresh chicken breasts. Overall, antimicrobial packaging shows promise as an effective method for the inhibition of certain bacteria in foods, but barriers to their commercial implementation continue to exist.

Gene-Specific Substitution Profiles Describe the Types and Frequencies of Amino Acid Changes during Antibody Somatic Hypermutation.

PubMed

Sheng, Zizhang; Schramm, Chaim A; Kong, Rui; Mullikin, James C; Mascola, John R; Kwong, Peter D; Shapiro, Lawrence

2017-01-01

Somatic hypermutation (SHM) plays a critical role in the maturation of antibodies, optimizing recognition initiated by recombination of V(D)J genes. Previous studies have shown that the propensity to mutate is modulated by the context of surrounding nucleotides and that SHM machinery generates biased substitutions. To investigate the intrinsic mutation frequency and substitution bias of SHMs at the amino acid level, we analyzed functional human antibody repertoires and developed mGSSP (method for gene-specific substitution profile), a method to construct amino acid substitution profiles from next-generation sequencing-determined B cell transcripts. We demonstrated that these gene-specific substitution profiles (GSSPs) are unique to each V gene and highly consistent between donors. We also showed that the GSSPs constructed from functional antibody repertoires are highly similar to those constructed from antibody sequences amplified from non-productively rearranged passenger alleles, which do not undergo functional selection. This suggests the types and frequencies, or mutational space, of a majority of amino acid changes sampled by the SHM machinery to be well captured by GSSPs. We further observed the rates of mutational exchange between some amino acids to be both asymmetric and context dependent and to correlate weakly with their biochemical properties. GSSPs provide an improved, position-dependent alternative to standard substitution matrices, and can be utilized to developing software for accurately modeling the SHM process. GSSPs can also be used for predicting the amino acid mutational space available for antigen-driven selection and for understanding factors modulating the maturation pathways of antibody lineages in a gene-specific context. The mGSSP method can be used to build, compare, and plot GSSPs; we report the GSSPs constructed for 69 common human V genes (DOI: 10.6084/m9.figshare.3511083) and provide high-resolution logo plots for each (DOI: 10.6084/m9.figshare.3511085).

In situ synthesis of magnesium-substituted biphasic calcium phosphate and in vitro biodegradation

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

Kim, Tae-Wan; Lee, Hyeong-Shin; Kim, Dong-Hyun

Highlights: ► Mg–BCP were successfully prepared through in situ aqueous co-precipitation method. ► The amount of β-TCP phase was changed with the magnesium substitution level. ► The substitution of magnesium led to a decrease in the unit cell volume. ► Mg–BCP could be able to develop a new apatite phase on the surface faster than BCP. -- Abstract: In situ preparation of magnesium (Mg) substituted biphasic calcium phosphate (BCP) of hydroxyapatite (HAp)/β-tricalcium phosphate (β-TCP) were carried out through aqueous co-precipitation method. The concentrations of added magnesium were varied with the calcium in order to obtain constant (Ca + Mg)/P ratiosmore » of 1.602. X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy were used to characterize the structure of synthesized magnesium substituted BCP powders. The results have shown that substitution of magnesium in the calcium deficient apatites revealed the formation of biphasic mixtures of different HAp/β-TCP ratios after heating at 1000 °C. The ratios of the formation of phase mixtures were dependent on the content of magnesium. After immersing in Hanks’ balanced salt solution (HBSS) for 1 week, 1 wt% magnesium substituted BCP powders were degraded and precipitation started to be formed with small granules consisting of number of flake-like crystal onto the surface of synthesized powders. On the other hand, in the case of pure BCP powders, the formation of new precipitates was detected after immersion in HBSS for 2 weeks. On the basis of these results, magnesium substituted BCP could be able to develop a new apatite phase on the surface in contact with physiological fluids faster than BCP does. In addition, the retention time to produce the new apatite phase in implantation operation for the BCP powder could be controlled by the amount of magnesium substitution.« less

Is snus the same as dip? Smokers’ perceptions of new smokeless tobacco advertising

PubMed Central

Bahreinifar, Sareh; Sheon, Nicolas M.; Ling, Pamela

2013-01-01

BACKGROUND Since 2006, leading US cigarette companies have been promoting new snus products as line extensions of popular cigarette brands. These promotional efforts include direct mail marketing to consumers on cigarette company mailing lists. This study examines smokers’ reactions to this advertising and perceptions of the new snus products. METHODS Eight focus groups (n=65 participants) were conducted in San Francisco and Los Angeles in 2010 with smokers who received tobacco direct mail advertising. The focus group discussions assessed smokers’ perceptions of the new snus products. Focus group videos were transcribed and coded using Transana software to identify common themes. RESULTS Most participants were aware of snus advertising and many had tried free samples. Most were aware snus was supposed to be “different” from traditional chewing tobacco, but did not consistently know why. Participants willing to try snus still identified strongly as smokers and for some, trying snus reinforced their preference for smoking. Snus’ major benefits were use in smokefree environments and avoiding social stigma related to secondhand smoke. Participants were skeptical of the idea that snus was safer than cigarettes, and did not see it as an acceptable substitute for cigarettes or as a cessation aid. CONCLUSION Smokers repeated some messages featured in early snus advertising. Snus was not seen as an acceptable substitute for smoking or way to quit cigarettes. Current smoker responses to snus advertising are not consistent with harm reduction. PMID:21972063

Four Chemical Trends Will Shape the Next Decade's Directions in Perfluoroalkyl and Polyfluoroalkyl Substances Research.

PubMed

Kotthoff, Matthias; Bücking, Mark

2018-01-01

Per- and polyfluoroalkyl substances (PFAS) represent a versatile group of ubiquitously occurring chemicals of increasing regulatory concern. The past years lead to an ever expanding portfolio of detected anthropogenic PFAS in numerous products encountered in daily life. Yet no clear picture of the full range of individual substance that comprise PFAS is available and this challenges analytical and engineering sciences. Authorities struggle to cope with uncertainties in managing risk of harm posed by PFAS. This is a result of an incomplete understanding of the range of compounds that they comprise in differing products. There are analytical uncertainties identifying PFAS and estimating the concentrations of the total PFAS load individual molecules remain unknown. There are four major trends from the chemical perspective that will shape PFAS research for the next decade. Mobility: A wide and dynamic distribution of short chain PFAS due to their high polarity, persistency and volatility.Substitution of regulated substances: The ban or restrictions of individual molecules will lead to a replacement with substitutes of similar concern.Increase in structural diversity of existing PFAS molecules: Introduction of e.g., hydrogens and chlorine atoms instead of fluorine, as well as branching and cross-linking lead to a high versatility of unknown target molecules.Unknown "Dark Matter": The amount, identity, formation pathways, and transformation dynamics of polymers and PFAS precursors are largely unknown. These directions require optimized analytical setups, especially multi-methods, and semi-specific tools to determine PFAS-sum parameters in any relevant matrix.

Four Chemical Trends Will Shape the Next Decade's Directions in Perfluoroalkyl and Polyfluoroalkyl Substances Research

PubMed Central

Kotthoff, Matthias; Bücking, Mark

2018-01-01

Per- and polyfluoroalkyl substances (PFAS) represent a versatile group of ubiquitously occurring chemicals of increasing regulatory concern. The past years lead to an ever expanding portfolio of detected anthropogenic PFAS in numerous products encountered in daily life. Yet no clear picture of the full range of individual substance that comprise PFAS is available and this challenges analytical and engineering sciences. Authorities struggle to cope with uncertainties in managing risk of harm posed by PFAS. This is a result of an incomplete understanding of the range of compounds that they comprise in differing products. There are analytical uncertainties identifying PFAS and estimating the concentrations of the total PFAS load individual molecules remain unknown. There are four major trends from the chemical perspective that will shape PFAS research for the next decade. Mobility: A wide and dynamic distribution of short chain PFAS due to their high polarity, persistency and volatility.Substitution of regulated substances: The ban or restrictions of individual molecules will lead to a replacement with substitutes of similar concern.Increase in structural diversity of existing PFAS molecules: Introduction of e.g., hydrogens and chlorine atoms instead of fluorine, as well as branching and cross-linking lead to a high versatility of unknown target molecules.Unknown “Dark Matter”: The amount, identity, formation pathways, and transformation dynamics of polymers and PFAS precursors are largely unknown. These directions require optimized analytical setups, especially multi-methods, and semi-specific tools to determine PFAS-sum parameters in any relevant matrix. PMID:29675408

Low-level radioactive waste management handbook series: Low-level radioactive waste management in medical and biomedical research institutions

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

Not Available

1987-03-01

Development of this handbook began in 1982 at the request of the Radhealth Branch of the California Department of Health Services. California Assembly Bill 1513 directed the DHS to ''evaluate the technical and economic feasibility of (1) reducing the volume, reactivity, and chemical and radioactive hazard of (low-level radioactive) waste and (2) substituting nonradioactive or short-lived radioactive materials for those radionuclides which require long-term isolation from the environment. A contract awarded to the University of California at Irvine-UCI (California Std. Agreement 79902), to develop a document focusing on methods for decreasing low-level radioactive waste (LLW) generation in institutions was amore » result of that directive. In early 1985, the US Department of Energy, through EG and G Idaho, Inc., contracted with UCI to expand, update, and revise the California text for national release.« less

Effect of adding Te to layered GaSe crystals to increase the van der Waals bonding force

NASA Astrophysics Data System (ADS)

Tanabe, Tadao; Zhao, Shu; Sato, Yohei; Oyama, Yutaka

2017-10-01

The interplanar binding strength of layered GaSe1-xTex crystals was directly measured using a tensile testing machine. The GaSe1-xTex crystals were grown by a low temperature liquid phase solution method under a controlled Se vapor pressure. The stoichiometry-controlled GaSe1-xTex crystal has the ɛ-polytype structure of GaSe, where the Te atoms are substituted for some of the Se atoms in the GaSe crystal. The effect of adding Te on the bonding strength between the GaSe layers was determined from direct measurements of the van der Waals bonding energy. The bonding energy was increased from 0.023 × 106 N/m2 for GaSe to 0.16 × 106 N/m2 for GaSe1-xTex (x = 0.106).

40 CFR 721.2077 - Substituted carbazate (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... death. This concern is particularly true with respect to direct contact to the eyes. Exposure to the eyes may cause severe acute toxicity including death. (ii) Industrial, commercial, and consumer...

40 CFR 721.2077 - Substituted carbazate (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... death. This concern is particularly true with respect to direct contact to the eyes. Exposure to the eyes may cause severe acute toxicity including death. (ii) Industrial, commercial, and consumer...

Effect of leucine-to-methionine substitutions on the diffraction quality of histone chaperone SET/TAF-Ibeta/INHAT crystals.

PubMed

Senda, Miki; Muto, Shinsuke; Horikoshi, Masami; Senda, Toshiya

2008-10-01

One of the most frequent problems in crystallization is poor quality of the crystals. In order to overcome this obstacle several methods have been utilized, including amino-acid substitutions of the target protein. Here, an example is presented of crystal-quality improvement by leucine-to-methionine substitutions. A variant protein with three amino-acid substitutions enabled improvement of the crystal quality of the histone chaperone SET/TAF-Ibeta/INHAT when combined with optimization of the cryoconditions. This procedure improved the resolution of the SET/TAF-Ibeta/INHAT crystals from around 5.5 to 2.3 A without changing the crystallization conditions.

The importance of four histidine residues in isocitrate lyase from Escherichia coli.

PubMed Central

Diehl, P; McFadden, B A

1994-01-01

By site-directed mutagenesis, substitutions were made for His-184 (H-184), H-197, H-266, and H-306 in Escherichia coli isocitrate lyase. Of these changes, only mutations of H-184 and H-197 appreciably reduced enzyme activity. Mutation of H-184 to Lys, Arg, or Leu resulted in an inactive isocitrate lyase, and mutation of H-184 to Gln resulted in an enzyme with 0.28% activity. Nondenaturing polyacrylamide gel electrophoresis demonstrated that isocitrate lyase containing the Lys, Arg, Gln, and Leu substitutions at H-184 was assembled poorly into the tetrameric subunit complex. Mutation of H-197 to Lys, Arg, Leu, and Gln resulted in an assembled enzyme with less than 0.25% wild-type activity. Five substitutions for H-266 (Asp, Glu, Val, Ser, and Lys), four substitutions for H-306 (Asp, Glu, Val, and Ser), and a variant in which both H-266 and H-306 were substituted for showed little or no effect on enzyme activity. All the H-197, H-266, and H-306 mutants supported the growth of isocitrate lyase-deficient E. coli JE10 on acetate as the sole carbon source; however, the H-184 mutants did not. Images PMID:8300547

Structural evolution of luciferase activity in Zophobas mealworm AMP/CoA-ligase (protoluciferase) through site-directed mutagenesis of the luciferin binding site.

PubMed

Prado, R A; Barbosa, J A; Ohmiya, Y; Viviani, V R

2011-07-01

The structural origin and evolution of bioluminescent activity of beetle luciferases from AMP/CoA ligases remains a mystery. Previously we cloned the luciferase-like enzyme from Zophobas morio mealworm, a reasonable protoluciferase model that could shine light on this mystery. Kinetic characterization and studies with D- and L-luciferin and their adenylates showed that stereoselectivity constitutes a critical feature for the origin of luciferase activity in AMP/CoA ligases. Comparison of the primary structures and modeling studies of this protoluciferase and the three main families of beetle luciferases showed that the carboxylic acid substrate binding site of this enzyme is smaller and more hydrophobic than the luciferin binding site of beetle luciferases, showing several substitutions of otherwise conserved residues. Thus, here we performed a site-directed mutagenesis survey of the carboxylic binding site motifs of the protoluciferase by replacing their residues by the respective conserved ones found in beetle luciferases in order to identify the structural determinants of luciferase/oxygenase activity. Although most of the substitutions had negative impact on the luminescence activity of the protoluciferase, only the substitution I327T improved the luminescence activity, resulting in a broad and 15 nm blue-shifted luminescence spectrum. Such substitution indicates the importance of the loop motif 322YGMSEI327 (341YGLTETT347 in Photinus pyralis luciferase) for luciferase activity, and indicates a possible route for the evolution of bioluminescence function of beetle luciferases.

Ion-substituted calcium phosphate coatings deposited by plasma-assisted techniques: A review.

PubMed

Graziani, Gabriela; Bianchi, Michele; Sassoni, Enrico; Russo, Alessandro; Marcacci, Maurilio

2017-05-01

One of the main critical aspects behind the failure or success of an implant resides in its ability to fast bond with the surrounding bone. To boost osseointegration, the ideal implant material should exhibit composition and structure similar to those of biological apatite. To this aim, the most common approach is to coat the implant surface with a coating of hydroxyapatite (HA), resembling the main component of mineralized tissues. However, bone apatite is a non-stoichiometric, multi-substituted poorly-crystalline apatite, containing significant amounts of foreign ions, with high biological relevance. Ion-substituted HAs can be deposited by so called "wet methods", which are however poorly reproducible and hardly industrially feasible; at the same time bioactive coatings realized by plasma assisted method, interesting for industrial applications, are generally made of stoichiometric (i.e. un-substituted) HA. In this work, the literature concerning plasma-assisted deposition methods used to deposit ion-substituted HA was reviewed and the last advances in this field discussed. The ions taken into exam are those present in mineralized tissues and possibly having biological relevance. Notably, literature about this topic is scarce, especially relating to in vivo animal and clinical trials; further on, available studies evaluate the performance of substituted coatings from different points of view (mechanical properties, bone growth, coating dissolution, etc.) which hinders a proper evaluation of the real efficacy of ion-doped HA in promoting bone regeneration, compared to stoichiometric HA. Moreover, results obtained for plasma sprayed coatings (which is the only method currently employed for deposition at the industrial scale) were collected and compared to those of novel plasma-assisted techniques, that are expected to overcome its limitations. Data so far available on the topic were discussed to highlight advantages, limitations and possible perspectives of these procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

Immunochemical Methods for Quantitation of Vitamin B6

DTIC Science & Technology

1981-09-30

pANk K:E:: Z P a . LIST OF FIGURES Page Figure 1. Synthesis of N-Carboxymethylpyridoxine 15 Figure 2. Pyridoxine and N- Substituted Derivatives 16...Pyridoxine Substituted in the 3 Position 23 Figure 6. Synthesis of as -Pyridoxylformic Acid and as - 25 Pyridoxylacetic Acid Figure 7. Fluorogenic Galactosides...CH20 (Vill) (X Figure 2. Pyridoxine and N- Substituted Derivatives 16 hinder the formation of quaternary salts (Kirpal, 1910).’" We found this to be true

Improved methodologies for the preparation of highly substituted pyridines.

PubMed

Fernández Sainz, Yolanda; Raw, Steven A; Taylor, Richard J K

2005-11-25

[reaction: see text] Two separate strategies have been developed for the preparation of highly substituted pyridines from 1,2,4-triazines via the inverse-electron-demand Diels-Alder reaction: a microwave-promoted, solvent-free procedure and a tethered imine-enamine (TIE) approach. Both routes avoid the need for a discrete aromatization step and offer significant advantages over the classical methods, giving a wide variety of tri-, tetra-, and penta-substituted pyridines in high, optimized yields.

Base-promoted one-pot tandem reaction of 3-(1-alkynyl)chromones under microwave irradiation to functionalized amino-substituted xanthones.

PubMed

Liu, Yang; Huang, Liping; Xie, Fuchun; Hu, Youhong

2010-09-17

A base-promoted one-pot tandem reaction has been developed from 3-(1-alkynyl)chromones with various acetonitriles to afford functionalized amino-substituted xanthones 3 under microwave irradiation. This tandem process involves multiple reactions, such as Michael addition/cyclization/1,2-addition, without a transition metal catalyst. This method provides an efficient approach to build up natural product-like diversified amino-substituted xanthone scaffolds rapidly.

Synthetic versatility of 2-substituted-6-methyl 2,3-dihydropyridinones in the synthesis of polyfunctional piperidine-based compounds and related β amino acid derivatives.

PubMed

Yang, Yang; Hardman, Clayton

2017-10-18

Chiral 2-substituted-6-methyl 2,3-dihydropyidinones 9, which can be facilely obtained from an asymmetric vinylogous Mannich reaction (VMR) with 1,3-bis-trimethysily enol ether, were used as versatile intermediates in constructing chiral polyfunctional piperidine-based compounds. The 6-methyl group of such compounds can be conveniently functionalized via alkylation and acylation reactions to provide efficient entries to the synthesis of a variety of chiral multi-substituted piperidine-based compounds. Further elaboration of the corresponding intermediates also provided access to polyfunctional indolizidine-based compounds. These methods were showcased in an asymmetric synthesis of 2,6-di-substituted piperidine compound 13, reported as the key intermediate in the synthesis of (+)-calvine and a natural alkaloid (-)-indolizidine 209D. Furthermore, selective C5 iodination of compound 9 enabled the installation of additional functional groups at this position. Finally, we demonstrated that the oxidative cleavage of 2-substituted-6-methyl-2,3-dihydropyidinones is a practical and efficient method for the enantioselective synthesis of β-amino acids, which can undergo further intra-molecular cyclization to give the corresponding chiral four-membered β-lactam derivatives.

Fabrication of Co0.5Ni0.5CrxFe2-xO4 materials via sol-gel method and their characterizations

NASA Astrophysics Data System (ADS)

Kadam, R. H.; Birajdar, A. P.; Alone, Suresh T.; Shirsath, Sagar E.

2013-02-01

Co0.5Ni0.5CrxFe2-xO4 nanoparticles have been designed by the sol-gel auto combustion method, using nitrates of the respective metal ions, and citric acid as the starting materials. The process takes only a few minutes to obtain as-received Cr-substituted Co-Ni ferrite powders. X-ray diffraction (XRD), vibrational sample magnetometer (VSM), transmission electron microscopy (TEM) are utilized in order to study the effect of variation in the Cr3+ substitution and its impact on particle size, lattice constant, specific surface area, cation distribution and magnetic properties. Lattice parameter, particle size found to decrease with increasing Cr3+ content, whereas specific surface area showed increasing trend with the Cr3+ substitution. Cation distribution indicates that the Cr, Co and Ni ions show preference toward octahedral [B] site, whereas Fe occupies both tetrahedral (A) and octahedral [B] sites. Saturation magnetization (MS) decreased from 65.1 to 40.6 emu/g with the increase in Cr3+ substitution. However, Coercivity increased from 198 to 365 Oe with the Cr3+ substitution.

[Regression on order statistics and its application in estimating nondetects for food exposure assessment].

PubMed

Yu, Xiaojin; Liu, Pei; Min, Jie; Chen, Qiguang

2009-01-01

To explore the application of regression on order statistics (ROS) in estimating nondetects for food exposure assessment. Regression on order statistics was adopted in analysis of cadmium residual data set from global food contaminant monitoring, the mean residual was estimated basing SAS programming and compared with the results from substitution methods. The results show that ROS method performs better obviously than substitution methods for being robust and convenient for posterior analysis. Regression on order statistics is worth to adopt,but more efforts should be make for details of application of this method.

A Microplate Format Assay for Real-Time Screening for New Aldolases that Accept Aryl-Substituted Acceptor Substrates.

PubMed

Ma, Huan; Enugala, Thilak Reddy; Widersten, Mikael

2015-12-01

Aldolases are potentially important biocatalysts for asymmetric synthesis of polyhydroxylated compounds. Fructose 6-phosphate aldolase (FSA) is of particular interest by virtue of its unusually relaxed dependency on phosphorylated substrates. FSA has been reported to be a promising catalyst of aldol addition involving aryl-substituted acceptors such as phenylacetaldehyde that can react with donor ketones such as hydroxyacetone. Improvement of the low intrinsic activity with bulky acceptor substrates of this type is of great interest but has been hampered by the lack of powerful screening protocols applicable in directed evolution strategies. Here we present a new screen allowing for direct spectrophotometric recording of retro-aldol cleavage. The assay utilizes an aldehyde reductase produced in vitro by directed evolution; it reduces the aldehyde product formed after cleavage of the aldol by FSA. The assay is suitable both for steady-state enzyme kinetics and for real-time activity screening in a 96-well format. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanistic Characterization and Molecular Modeling of Hepatitis B Virus Polymerase Resistance to Entecavir

PubMed Central

Walsh, Ann W.; Langley, David R.; Colonno, Richard J.; Tenney, Daniel J.

2010-01-01

Background Entecavir (ETV) is a deoxyguanosine analog competitive inhibitor of hepatitis B virus (HBV) polymerase that exhibits delayed chain termination of HBV DNA. A high barrier to entecavir-resistance (ETVr) is observed clinically, likely due to its potency and a requirement for multiple resistance changes to overcome suppression. Changes in the HBV polymerase reverse-transcriptase (RT) domain involve lamivudine-resistance (LVDr) substitutions in the conserved YMDD motif (M204V/I ± L180M), plus an additional ETV-specific change at residues T184, S202 or M250. These substitutions surround the putative dNTP binding site or primer grip regions of the HBV RT. Methods/Principal Findings To determine the mechanistic basis for ETVr, wildtype, lamivudine-resistant (M204V, L180M) and ETVr HBVs were studied using in vitro RT enzyme and cell culture assays, as well as molecular modeling. Resistance substitutions significantly reduced ETV incorporation and chain termination in HBV DNA and increased the ETV-TP inhibition constant (Ki) for HBV RT. Resistant HBVs exhibited impaired replication in culture and reduced enzyme activity (kcat) in vitro. Molecular modeling of the HBV RT suggested that ETVr residue T184 was adjacent to and stabilized S202 within the LVDr YMDD loop. ETVr arose through steric changes at T184 or S202 or by disruption of hydrogen-bonding between the two, both of which repositioned the loop and reduced the ETV-triphosphate (ETV-TP) binding pocket. In contrast to T184 and S202 changes, ETVr at primer grip residue M250 was observed during RNA-directed DNA synthesis only. Experimentally, M250 changes also impacted the dNTP-binding site. Modeling suggested a novel mechanism for M250 resistance, whereby repositioning of the primer-template component of the dNTP-binding site shifted the ETV-TP binding pocket. No structural data are available to confirm the HBV RT modeling, however, results were consistent with phenotypic analysis of comprehensive substitutions of each ETVr position. Conclusions Altogether, ETVr occurred through exclusion of ETV-TP from the dNTP-binding site, through different, novel mechanisms that involved lamivudine-resistance, ETV-specific substitutions, and the primer-template. PMID:20169198

Role of A-site Ca and B-site Zr substitution in BaTiO3 lead-free compounds: Combined experimental and first principles density functional theoretical studies

NASA Astrophysics Data System (ADS)

Keswani, Bhavna C.; Saraf, Deepashri; Patil, S. I.; Kshirsagar, Anjali; James, A. R.; Kolekar, Y. D.; Ramana, C. V.

2018-05-01

We report on the combined experimental and theoretical simulation results of lead-free ferroelectrics, Ba(1-x)CaxTiO3 (x = 0.0-0.3) and BaTi(1-y)ZryO3 (y = 0.0-0.2), synthesized by standard solid state reaction method. First principles density functional calculations are used to investigate the electronic structure, dynamical charges, and spontaneous polarization of these compounds. In addition, the structural, ferroelectric, piezoelectric, and dielectric properties are studied using extensive experiments. The X-ray diffraction and temperature dependent Raman spectroscopy studies indicate that the calcium (Ca) substituted compositions exhibit a single phase crystal structure, while zirconium (Zr) substituted compositions are biphasic. The scanning electron micrographs reveal the uniform and highly dense microstructure. The presence of polarization-electric field and strain-electric field hysteresis loops confirms the ferroelectric and piezoelectric nature of all the compositions. Our results demonstrate higher values for polarization, percentage strain, piezoelectric coefficients, and electrostrictive coefficient compared to those existing in the literature. For smaller substitutions of Ca and Zr in BaTiO3, a direct piezoelectric coefficient (d33) is enhanced, while the highest d33 value (˜300 pC/N) is observed for BaTi0.96Zr0.04O3 due to the biphasic ferroelectric behavior. Calculation of Born effective charges indicates that doping with Ca or Zr increases the dynamical charges on Ti as well as on O and decreases the dynamical charge on Ba. An increase in the dynamical charges on Ti and O is ascribed to the increase in covalency of Ti-O bond that reduces the polarizability of the crystal. A broader range of temperatures is demonstrated to realize the stable phase in the Ca substituted compounds. The results indicate enhancement in the temperature range of applicability of these compounds for device applications. The combined theoretical and experimental study is expected to enhance the current scientific understanding of the lead-free ferroelectric materials.

Prediction of CT Substitutes from MR Images Based on Local Diffeomorphic Mapping for Brain PET Attenuation Correction.

PubMed

Wu, Yao; Yang, Wei; Lu, Lijun; Lu, Zhentai; Zhong, Liming; Huang, Meiyan; Feng, Yanqiu; Feng, Qianjin; Chen, Wufan

2016-10-01

Attenuation correction is important for PET reconstruction. In PET/MR, MR intensities are not directly related to attenuation coefficients that are needed in PET imaging. The attenuation coefficient map can be derived from CT images. Therefore, prediction of CT substitutes from MR images is desired for attenuation correction in PET/MR. This study presents a patch-based method for CT prediction from MR images, generating attenuation maps for PET reconstruction. Because no global relation exists between MR and CT intensities, we propose local diffeomorphic mapping (LDM) for CT prediction. In LDM, we assume that MR and CT patches are located on 2 nonlinear manifolds, and the mapping from the MR manifold to the CT manifold approximates a diffeomorphism under a local constraint. Locality is important in LDM and is constrained by the following techniques. The first is local dictionary construction, wherein, for each patch in the testing MR image, a local search window is used to extract patches from training MR/CT pairs to construct MR and CT dictionaries. The k-nearest neighbors and an outlier detection strategy are then used to constrain the locality in MR and CT dictionaries. Second is local linear representation, wherein, local anchor embedding is used to solve MR dictionary coefficients when representing the MR testing sample. Under these local constraints, dictionary coefficients are linearly transferred from the MR manifold to the CT manifold and used to combine CT training samples to generate CT predictions. Our dataset contains 13 healthy subjects, each with T1- and T2-weighted MR and CT brain images. This method provides CT predictions with a mean absolute error of 110.1 Hounsfield units, Pearson linear correlation of 0.82, peak signal-to-noise ratio of 24.81 dB, and Dice in bone regions of 0.84 as compared with real CTs. CT substitute-based PET reconstruction has a regression slope of 1.0084 and R 2 of 0.9903 compared with real CT-based PET. In this method, no image segmentation or accurate registration is required. Our method demonstrates superior performance in CT prediction and PET reconstruction compared with competing methods. © 2016 by the Society of Nuclear Medicine and Molecular Imaging, Inc.

Theoretical effects of substituting butter with margarine on risk of cardiovascular disease

PubMed Central

Liu, Qing; Rossouw, Jacques E.; Roberts, Mary B.; Liu, Simin; Johnson, Karen C.; Shikany, James M.; Manson, JoAnn E.; Tinker, Lesley F.; Eaton, Charles B.

2017-01-01

Background Several recent papers have called into question the deleterious effects of high animal fat diets due to mixed results from epidemiologic studies and the lack of clinical trial evidence in meta-analyses of dietary intervention trials. We were interested in examining the theoretical effects of substituting plant-based fats from different types of margarine for animal based fat from butter on the risk of atherosclerosis-related cardiovascular disease (CVD). Methods We prospectively studied 71,410 women, aged 50–79 years, and evaluated their risk for clinical myocardial infarction (MI), total coronary heart disease (CHD), ischemic stroke and atherosclerosis-related CVD with an average of 13.2 years of follow-up. Butter and margarine intakes were obtained at baseline and Year 3 by means of a validated food frequency questionnaire. Cox proportional hazards regression using a cumulative average diet method was used to estimate the theoretical effect of substituting 1 teaspoon/day of three types of margarine for the same amount of butter. Results Substituting butter or stick margarine with tub margarine was associated with lower risk of MI (HRs=0.95 and 0.91). Subgroup analyses, which evaluated these substitutions among participants with a single source of spreadable fat, showed stronger associations for MI (HRs=0.92 and 0.87). Outcomes of total CHD, ischemic stroke, and atherosclerosis-related CVD showed wide confidence intervals but the same trends as the MI results. Conclusions This theoretical dietary substitution analysis suggests that substituting butter and stick margarine with tub margarine when spreadable fats are eaten may be associated with reduced risk of myocardial infarction. PMID:27648593

Ferromagnetism of Fe 3Sn and alloys

DOE PAGES

Sales, Brian C.; Saparov, Bayrammurad; McGuire, Michael A.; ...

2014-11-12

Hexagonal Fe 3Sn has many of the desirable properties for a new permanent magnet phase with a Curie temperature of 725 K, a saturation moment of 1.18 MA/m. and anisotropy energy, K 1 of 1.8 MJ/m 3. However, contrary to earlier experimental reports, we found both experimentally and theoretically that the easy magnetic axis lies in the hexagonal plane, which is undesirable for a permanent magnet material. One possibility for changing the easy axis direction is through alloying. We used first principles calculations to investigate the effect of elemental substitutions. The calculations showed that substitution on the Sn site hasmore » the potential to switch the easy axis direction. Transition metal substitutions with Co or Mn do not have this effect. We attempted synthesis of a number of these alloys and found results in accord with the theoretical predictions for those that were formed. However, the alloys that could be readily made all showed an in-plane easy axis. The electronic structure of Fe 3Sn is reported, as are some are magnetic and structural properties for the Fe 3Sn 2, and Fe 5Sn 3 compounds, which could be prepared as mm-sized single crystals.« less

A comparative study of rhodopsin function in the great bowerbird (P tilonorhynchus nuchalis): Spectral tuning and light‐activated kinetics

PubMed Central

van Hazel, Ilke; Dungan, Sarah Z.; Hauser, Frances E.; Morrow, James M.; Endler, John A.

2016-01-01

Abstract Rhodopsin is the visual pigment responsible for initiating the phototransduction cascade in vertebrate rod photoreceptors. Although well‐characterized in a few model systems, comparative studies of rhodopsin function, particularly for nonmammalian vertebrates are comparatively lacking. Bowerbirds are rare among passerines in possessing a key substitution, D83N, at a site that is otherwise highly conserved among G protein‐coupled receptors. While this substitution is present in some dim‐light adapted vertebrates, often accompanying another unusual substitution, A292S, its functional relevance in birds is uncertain. To investigate functional effects associated with these two substitutions, we use the rhodopsin gene from the great bowerbird (Ptilonorhynchus nuchalis) as a background for site‐directed mutagenesis, in vitro expression and functional characterization. We also mutated these sites in two additional rhodopsins that do not naturally possess N83, chicken and bovine, for comparison. Both sites were found to contribute to spectral blue‐shifts, but had opposing effects on kinetic rates. Substitutions at site 83 were found to primarily affect the kinetics of light‐activated rhodopsin, while substitutions at site 292 had a larger impact on spectral tuning. The contribution of substitutions at site 83 to spectral tuning in particular depended on genetic background, but overall, the effects of substitutions were otherwise surprisingly additive, and the magnitudes of functional shifts were roughly similar across all three genetic backgrounds. By employing a comparative approach with multiple species, our study provides new insight into the joint impact of sites 83 and 292 on rhodopsin structure‐function as well as their evolutionary significance for dim‐light vision across vertebrates. PMID:26889650

A comparative study of rhodopsin function in the great bowerbird (Ptilonorhynchus nuchalis): Spectral tuning and light-activated kinetics.

PubMed

van Hazel, Ilke; Dungan, Sarah Z; Hauser, Frances E; Morrow, James M; Endler, John A; Chang, Belinda S W

2016-07-01

Rhodopsin is the visual pigment responsible for initiating the phototransduction cascade in vertebrate rod photoreceptors. Although well-characterized in a few model systems, comparative studies of rhodopsin function, particularly for nonmammalian vertebrates are comparatively lacking. Bowerbirds are rare among passerines in possessing a key substitution, D83N, at a site that is otherwise highly conserved among G protein-coupled receptors. While this substitution is present in some dim-light adapted vertebrates, often accompanying another unusual substitution, A292S, its functional relevance in birds is uncertain. To investigate functional effects associated with these two substitutions, we use the rhodopsin gene from the great bowerbird (Ptilonorhynchus nuchalis) as a background for site-directed mutagenesis, in vitro expression and functional characterization. We also mutated these sites in two additional rhodopsins that do not naturally possess N83, chicken and bovine, for comparison. Both sites were found to contribute to spectral blue-shifts, but had opposing effects on kinetic rates. Substitutions at site 83 were found to primarily affect the kinetics of light-activated rhodopsin, while substitutions at site 292 had a larger impact on spectral tuning. The contribution of substitutions at site 83 to spectral tuning in particular depended on genetic background, but overall, the effects of substitutions were otherwise surprisingly additive, and the magnitudes of functional shifts were roughly similar across all three genetic backgrounds. By employing a comparative approach with multiple species, our study provides new insight into the joint impact of sites 83 and 292 on rhodopsin structure-function as well as their evolutionary significance for dim-light vision across vertebrates. © 2016 The Protein Society.

Can Cannabis be Considered a Substitute Medication for Alcohol?

PubMed Central

Subbaraman, Meenakshi Sabina

2014-01-01

Aims: Substituting cannabis for alcohol may reduce drinking and related problems among alcohol-dependent individuals. Some even recommend prescribing medical cannabis to individuals attempting to reduce drinking. The primary aim of this review is to assess whether cannabis satisfies the seven previously published criteria for substitute medications for alcohol [e.g. ‘reduces alcohol-related harms’; ‘is safer in overdose than alcohol’; ‘should offer significant health economic benefits’; see Chick and Nutt ((2012) Substitution therapy for alcoholism: time for a reappraisal? J Psychopharmacol 26:205–12)]. Methods: Literature review. Results: All criteria appear either satisfied or partially satisfied, though studies relying on medical cannabis patients may be limited by selection bias and/or retrospective designs. Individual-level factors, such as severity of alcohol problems, may also moderate substitution. Conclusions: There is no clear pattern of outcomes related to cannabis substitution. Most importantly, the recommendation to prescribe alcohol-dependent individuals cannabis to help reduce drinking is premature. Future studies should use longitudinal data to better understand the consequences of cannabis substitution. PMID:24402247

Investigation of Sm substitution on structural and superconducting properties of Y1Ba2-xSmxCu3O7-δ superconductors

NASA Astrophysics Data System (ADS)

Sharifzadegan, L.; Sedghi, H.

2018-07-01

In this work, samples of a nominal composition Y1 Ba2 - x Smx Cu3O7 - δ With Sm substitution (X = 0.00, 0.01, 0.03, 0.05) were prepared by the solid state reaction method. And the effect of substituting Sm instead of Ba was investigated on the structural and superconducting properties of the samples. Measurement of electrical resistance and critical temperature was done using 4-Probe connection method. Results indicate that Sm substitution affects the YBSCO superconducting samples, decrease the transition temperature of the superconductor and increases the special electrical resistance and the transition width. Also, XRD studies show that in all samples of the Y-123 phase, the formation and structure is orthorhombic. SEM images showed that the porosity in the samples increased with increasing Sm due to disruption in grain growth and instead, increase Sm in the samples cause decreasing the size of the grain.

Freeze substitution in 3 hours or less.

PubMed

McDonald, K L; Webb, R I

2011-09-01

Freeze substitution is a process for low temperature dehydration and fixation of rapidly frozen cells that usually takes days to complete. New methods for freeze substitution have been developed that require only basic laboratory tools: a platform shaker, liquid nitrogen, a metal block with holes for cryotubes and an insulated container such as an ice bucket. With this equipment, excellent freeze substitution results can be obtained in as little as 90 min for cells of small volume such as bacteria and tissue culture cells. For cells of greater volume or that have significant diffusion barriers such as cuticles or thick cell walls, one can extend the time to 3 h or more with dry ice. The 3-h method works well for all manner of specimens, including plants and Caenorhabditis elegans as well as smaller samples. Here, we present the basics of the techniques and some results from Nicotiana leaves, C. elegans adult worms, Escherichia coli and baby hamster kidney tissue culture cells. © 2011 The Authors Journal of Microscopy © 2011 Royal Microscopical Society.

Determination of stream reaeration coefficients by use of tracers

USGS Publications Warehouse

Kilpatrick, F.A.; Rathbun, R.E.; Yotsukura, Nobuhiro; Parker, G.W.; DeLong, L.L.

1989-01-01

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes. Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed whereby a radioactive tracer gas was injected into a stream-the principle being that the tracer gas would be desorbed from the stream inversely to how oxygen would be absorbed. The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas. This manual describes the slug-injection and constant-rate-injection methods of measuring gas-tracer desorption. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, on methods of injection, sampling, and analysis, and on techniques for computing desorption and reaeration coefficients.

System and method for producing substitute natural gas from coal

DOEpatents

Hobbs, Raymond [Avondale, AZ

2012-08-07

The present invention provides a system and method for producing substitute natural gas and electricity, while mitigating production of any greenhouse gasses. The system includes a hydrogasification reactor, to form a gas stream including natural gas and a char stream, and an oxygen burner to combust the char material to form carbon oxides. The system also includes an algae farm to convert the carbon oxides to hydrocarbon material and oxygen.

Easy sellar reconstruction in endoscopic endonasal transsphenoidal surgery with polyester-silicone dural substitute and fibrin glue: technical note.

PubMed

Cappabianca, P; Cavallo, L M; Mariniello, G; de Divitiis, O; Romero, A D; de Divitiis, E

2001-08-01

To describe a simple method of sellar reconstruction after endoscopic endonasal transsphenoidal surgery that will allow rapid watertight closure of the sellar floor. A bent sheet of a polyester-silicone dural substitute, fashioned for this purpose with scissors, is introduced into the sella after removal of the lesion. Because of the consistency of the sheet, it opens spontaneously and becomes stuck. Autologous fat tissue or gelatin foam is positioned thereafter, followed by another layer of the dural substitute; a film of fibrin glue completes the sealing. Fifteen patients underwent this method and no postoperative cerebrospinal leak or other complication was experienced. This easy method of sellar reconstruction represents an effective and fast possibility to perform the final step of the endoscopic transsphenoidal procedure, which otherwise may cause maneuverability problems in the limited space of one nostril.

Electric Power Distribution System Model Simplification Using Segment Substitution

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

Reiman, Andrew P.; McDermott, Thomas E.; Akcakaya, Murat

Quasi-static time-series (QSTS) simulation is used to simulate the behavior of distribution systems over long periods of time (typically hours to years). The technique involves repeatedly solving the load-flow problem for a distribution system model and is useful for distributed energy resource (DER) planning. When a QSTS simulation has a small time step and a long duration, the computational burden of the simulation can be a barrier to integration into utility workflows. One way to relieve the computational burden is to simplify the system model. The segment substitution method of simplifying distribution system models introduced in this paper offers modelmore » bus reduction of up to 98% with a simplification error as low as 0.2% (0.002 pu voltage). In contrast to existing methods of distribution system model simplification, which rely on topological inspection and linearization, the segment substitution method uses black-box segment data and an assumed simplified topology.« less

Analysis of fatigue characteristic of sm-substituted DyFeCo magneto-optical films

NASA Astrophysics Data System (ADS)

Li, Zuoyi; Wang, Ke; Yang, Xiaofei; Li, Zhen; Lin, Gengqi

2003-04-01

The fatigue characteristic of the amorphous Sm-substituted DyFeCo magneto-optical alloy films fabricated by R.F. magnetron sputtering method were investigated by accelerated pulse training method under the condition of magnetic field modulation plus laser pulse irradiation. The evaluation of fatigue characteristic is determined from the static magneto-optical signal readout level after several writing/erasing repetitions compared with initial level. The experimental dependence of fatigue characteristics is in good agreement with the model based on the JMA equation. Furthermore, the Avrami factor can be derived from the model. Experimental results show that it is very effective in studying the writing/erasing ability of magneto-optical films employed the method of combined the accelerated pulse training with the JMA equation and Sm-substituted HRE-TM alloys can act as a practical medium for MO storage at short wavelength.

Estimation of descriptive statistics for multiply censored water quality data

USGS Publications Warehouse

Helsel, Dennis R.; Cohn, Timothy A.

1988-01-01

This paper extends the work of Gilliom and Helsel (1986) on procedures for estimating descriptive statistics of water quality data that contain “less than” observations. Previously, procedures were evaluated when only one detection limit was present. Here we investigate the performance of estimators for data that have multiple detection limits. Probability plotting and maximum likelihood methods perform substantially better than simple substitution procedures now commonly in use. Therefore simple substitution procedures (e.g., substitution of the detection limit) should be avoided. Probability plotting methods are more robust than maximum likelihood methods to misspecification of the parent distribution and their use should be encouraged in the typical situation where the parent distribution is unknown. When utilized correctly, less than values frequently contain nearly as much information for estimating population moments and quantiles as would the same observations had the detection limit been below them.

The role of forests in energy and climate change - integrating objectives

Treesearch

Dave Atkins

2010-01-01

Woody biomass utilization presents a tremendous opportunity to address energy independence directly through the use of domestic wood as an energy source that offsets fossil fuel. It also works indirectly through conservation by the substitution of wood for higher embodied energy construction materials such as concrete and steel. Both the direct and indirect measures...

Meaning From Environmental Sounds: Types of Signal-Referent Relations and Their Effect on Recognizing Auditory Icons

ERIC Educational Resources Information Center

Keller, Peter; Stevens, Catherine

2004-01-01

This article addresses the learnability of auditory icons, that is, environmental sounds that refer either directly or indirectly to meaningful events. Direct relations use the sound made by the target event whereas indirect relations substitute a surrogate for the target. Across 3 experiments, different indirect relations (ecological, in which…

The equivalence of numbers: The social value of avoiding health decline: An experimental web-based study

PubMed Central

Schwappach, David LB

2002-01-01

Background Health economic analysis aimed at informing policy makers and supporting resource allocation decisions has to evaluate not only improvements in health but also avoided decline. Little is known however, whether the "direction" in which changes in health are experienced is important for the public in prioritizing among patients. This experimental study investigates the social value people place on avoiding (further) health decline when directly compared to curative treatments in resource allocation decisions. Methods 127 individuals completed an interactive survey that was published in the World Wide Web. They were confronted with a standard gamble (SG) and three person trade-off tasks, either comparing improvements in health (PTO-Up), avoided decline (PTO-Down), or both, contrasting health changes of equal magnitude differing in the direction in which they are experienced (PTO-WAD). Finally, a direct priority ranking of various interventions was obtained. Results Participants strongly prioritized improving patients' health rather than avoiding decline. The mean substitution rate between health improvements and avoided decline (WAD) ranged between 0.47 and 0.64 dependent on the intervention. Weighting PTO values according to the direction in which changes in health are experienced improved their accuracy in predicting a direct prioritization ranking. Health state utilities obtained by the standard gamble method seem not to reflect social values in resource allocation contexts. Conclusion Results suggest that the utility of being cured of a given health state might not be a good approximation for the societal value of avoiding this health state, especially in cases of competition between preventive and curative interventions. PMID:11879529

Thick Smear is a Good Substitute for the Thin Smear in Parasitological Confirmation of Canine Visceral Leishmaniasis.

PubMed

de Mello, Cintia Xavier; Figueiredo, Fabiano Borges; Mendes Júnior, Artur Augusto Velho; Miranda, Luciana de Freitas Campos; de Oliveira, Raquel de Vasconcellos Carvalhaes; Madeira, Maria de Fátima

2016-07-06

Although direct examination methods are important for diagnosing leishmaniasis, such methods are often neglected because of their low sensitivity relative to other techniques. Our study aimed to evaluate the performance of bone marrow (BM) thick smears and cytocentrifugation tests as alternatives to direct examination for diagnosing canine visceral leishmaniasis (CVL). Ninety-two dogs exhibiting leishmaniasis seroreactivity were evaluated. The animals were euthanized; and healthy skin, spleen, popliteal lymph node, and BM puncture samples were cultured. BM cultures were used as the reference standard. Of the 92 dogs studied, 85.9% exhibited positive cultures, and Leishmania infantum (synonym Leishmania chagasi) was confirmed in all positive culture cases. The sensitivity rates for cytocentrifugation as well as thin and thick smears were 47.1%, 52.8%, and 77%, respectively. However, no association between the dogs' clinical status and culture or direct examination results was found. To our knowledge, this was the first study to use thick smears and cytocentrifugation for diagnosing CVL. Our results indicate that BM thick smears have a good sensitivity and their use reduces the time required to read slides. Therefore, thick smears can provide a rapid and safe alternative to parasitological confirmation of seroreactive dogs. © The American Society of Tropical Medicine and Hygiene.

Interference method for obtaining the potential flow past an arbitrary cascade of airfoils

NASA Technical Reports Server (NTRS)

Katzoff, S; Finn, Robert S; Laurence, James C

1947-01-01

A procedure is presented for obtaining the pressure distribution on an arbitrary airfoil section in cascade in a two-dimensional, incompressible, and nonviscous flow. The method considers directly the influence on a given airfoil of the rest of the cascade and evaluates this interference by an iterative process, which appeared to converge rapidly in the cases tried (about unit solidity, stagger angles of 0 degree and 45 degrees). Two variations of the basic interference calculations are described. One, which is accurate enough for most purposes, involves the substitution of sources, sinks, and vortices for the interfering airfoils; the other, which may be desirable for the final approximation, involves a contour integration. The computations are simplified by the use of a chart presented by Betz in a related paper. Illustrated examples are included.

Conservation: Toward firmer ground

NASA Technical Reports Server (NTRS)

1975-01-01

The following aspects of energy conservation were discussed: conservation history and goals, conservation modes, conservation accounting-criteria, and a method to overcome obstacles. The conservation modes tested fall into one of the following categories: reduced energy consumption, increased efficiency of energy utilization, or substitution of one or more forms of energy for another which is in shorter supply or in some sense thought to be of more value. The conservation accounting criteria include net energy reduction, economic, and technical criteria. A method to overcome obstacles includes (approaches such as: direct personal impact (life style, income, security, aspiration), an element of crisis, large scale involvement of environmental, safety, and health issues, connections to big government, big business, big politics, involvement of known and speculative science and technology, appeal to moral and ethical standards, the transient nature of opportunities to correct the system.

Difference structures from time-resolved small-angle and wide-angle x-ray scattering

NASA Astrophysics Data System (ADS)

Nepal, Prakash; Saldin, D. K.

2018-05-01

Time-resolved small-angle x-ray scattering/wide-angle x-ray scattering (SAXS/WAXS) is capable of recovering difference structures directly from difference SAXS/WAXS curves. It does so by means of the theory described here because the structural changes in pump-probe detection in a typical time-resolved experiment are generally small enough to be confined to a single residue or group in close proximity which is identified by a method akin to the difference Fourier method of time-resolved crystallography. If it is assumed, as is usual with time-resolved structures, that the moved atoms lie within the residue, the 100-fold reduction in the search space (assuming a typical protein has about 100 residues) allows the exaction of the structure by a simulated annealing algorithm with a huge reduction in computing time and leads to a greater resolution by varying the positions of atoms only within that residue. This reduction in the number of potential moved atoms allows us to identify the actual motions of the individual atoms. In the case of a crystal, time-resolved calculations are normally performed using the difference Fourier method, which is, of course, not directly applicable to SAXS/WAXS. The method developed in this paper may be thought of as a substitute for that method which allows SAXS/WAXS (and hence disordered molecules) to also be used for time-resolved structural work.

Evaluating the efficacy of a structure-derived amino acid substitution matrix in detecting protein homologs by BLAST and PSI-BLAST.

PubMed

Goonesekere, Nalin Cw

2009-01-01

The large numbers of protein sequences generated by whole genome sequencing projects require rapid and accurate methods of annotation. The detection of homology through computational sequence analysis is a powerful tool in determining the complex evolutionary and functional relationships that exist between proteins. Homology search algorithms employ amino acid substitution matrices to detect similarity between proteins sequences. The substitution matrices in common use today are constructed using sequences aligned without reference to protein structure. Here we present amino acid substitution matrices constructed from the alignment of a large number of protein domain structures from the structural classification of proteins (SCOP) database. We show that when incorporated into the homology search algorithms BLAST and PSI-blast, the structure-based substitution matrices enhance the efficacy of detecting remote homologs.

Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione.

PubMed

Lee, Jihoon; Panek, James S

2014-06-20

A sequential Diels-Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels-Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13.

Waste-free synthesis of condensed heterocyclic compounds by rhodium-catalyzed oxidative coupling of substituted arene or heteroarene carboxylic acids with alkynes.

PubMed

Shimizu, Masaki; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2009-05-01

The direct oxidative coupling of 2-amino- and 2-hydroxybenzoic acids with internal alkynes proceeds efficiently in the presence of a rhodium/copper catalyst system under air to afford the corresponding 8-substituted isocoumarin derivatives, some of which exhibit solid-state fluorescence. Depending on conditions, 4-ethenylcarbazoles can be synthesized selectively from 2-(arylamino)benzoic acids. The oxidative coupling reactions of heteroarene carboxylic acids as well as aromatic diacids with an alkyne are also described.

Pharmacists' views and reported practices in relation to a new generic drug substitution policy in Lebanon: a mixed methods study.

PubMed

El-Jardali, Fadi; Fadlallah, Racha; Morsi, Rami Z; Hemadi, Nour; Al-Gibbawi, Mounir; Haj, Magda; Khalil, Suzan; Saklawi, Youssef; Jamal, Diana; Akl, Elie A

2017-02-17

Governments in both developed and developing countries have adopted generic drug substitution policies to decrease pharmaceutical expenditures and improve access to medicine. In August 2015, the Ministry of Public Health (MOPH) in Lebanon introduced generic drug substitution and a unified medical prescription form as policy instruments to promote generic drug use. The objective of this exploratory study was to examine the attitudes of community pharmacists and the reported practices in relation to the implementation of the new generic drug substitution policy. We used a cross-sectional mixed methods approach composed of self-administered questionnaires and semi-structured interviews. The study population consisted of community pharmacists in Lebanon. We randomly approached one pharmacy personnel from each selected community pharmacy. We conducted descriptive analyses to assess responses to questionnaire and regression analyses to understand associations between responses and respondent demographics. We analyzed qualitative data thematically. Out of 204 invited community pharmacies, 153 pharmacies participated (75% response rate). The majority of respondents (64%) were in favor of generic drug substitution; however, less than half (40%) indicated they have substituted brand drugs for generic equivalents. Moreover, 57% indicated that the existing pricing system discourages them from performing generic drug substitution. Most respondents indicated that physicians are overusing the "non-substitutable" option (84%) and that there are technical problems with processing the new prescription form (78%). Less than half (47%) reported that the MOPH is performing regular audits on the forms collected by the pharmacy. While 45% of the respondents indicated that consumers have accepted most of the generic substitutions, 21% perceived the increase in generic drug dispensing to be significant. Findings suggested a potentially significant association between being informed about generic drugs and respondents' support of the policy. Suggested strategies to address implementation challenges included strengthening stewardship function of MOPH, securing full commitment of health care providers, conducting educational and awareness campaigns about generic drugs and generic drug substitution, and aligning incentive systems of the key stakeholders. The majority of community pharmacists were supportive of generic drug substitution in general but not of the current implementation of the policy in Lebanon. Findings revealed implementation challenges at the provider, patient, and system level which are hindering attainment of the policy objectives. The key lessons derived from this study can be used for continuous improvement of the policy and its implementation.

Raman Spectroscopy of Water-rich Stishovite and Dense High-Pressure Silica up to 55 GPa

NASA Astrophysics Data System (ADS)

Nisr, C.; Shim, S. H.; Leinenweber, K. D.; Chizmeshya, A. V.

2017-12-01

Recent studies have shown that mineral phases such as δ-AlOOH, (Mg,Si)OOH, (Mg,Si,Al)OOH, (Al,Si)O2 and SiO2 with rutile-type or modified rutile-type crystal structures can store large amounts of water and be stable at high pressure and high temperature relevant to the Earth's lower mantle. The Al-H charge coupled substitution has been proposed to explain the large storage capacity of these phases. However, the substitution cannot explain the large water storage found in pure stishovite (Spektor et al., 2011). Instead, an octahedral version of hydrogarnet-like substitution has been proposed for the incorporation of hydrogen in pure stishovite. We have performed Raman spectroscopy measurements on pure hydrous stishovite with 3.2 wt% water up to 55 GPa. At ambient pressure, we found that the OH stretching mode frequencies range between those of low-water aluminous stishovite and δ-AlOOH, suggesting an intermediate strength of hydrogen bonding between these two phases. In the lattice mode range, we observe modes similar to the IR-active modes of anhydrous stishovite after decompression to 1 bar, suggesting Si defects in the crystal structure that activate the inactive modes. Our data show a series of changes at pressures between 24 and 28 GPa, supporting our observation of a phase transition (likely to the CaCl2 type) in X-Ray diffraction measurements (Nisr et al., 2017, JGR). We found that the OH mode of hydrous stishovite has a positive frequency shift with an increase in pressure. The behavior is the opposite to that found in δ-AlOOH, indicating that the OH incorporation mechanism in hydrous silica is different from that of aluminous low-water stishovite and δ-AlOOH, likely through direct substitution (Si ⇄ 4H+). Because the mantle hydrous phases would have complex compositions, our study suggests that the direct substitution should also be considered together with the Al substitution for the deep mantle storage of water.

A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies.

PubMed

Vilella, Laia; Conde, Ana; Balcells, David; Díaz-Requejo, M Mar; Lledós, Agustí; Pérez, Pedro J

2017-12-01

A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, Tp x Cu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tp x = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu-O moiety prior to the C-O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured.

The Impact of Marketing of Breast-Milk Substitutes on WHO-Recommended Breastfeeding Practices.

PubMed

Piwoz, Ellen G; Huffman, Sandra L

2015-12-01

Suboptimal breastfeeding results in 800 000 child deaths annually. There are multiple causes of suboptimal breastfeeding, including marketing of breast-milk substitutes. To describe sales and marketing of breast-milk substitutes and their influence on World Health Organization-recommended breastfeeding behaviors, focusing on low- and middle-income countries. Literature review. Global sales of breast-milk substitutes reached US$40 billion in 2013. Growth in sales exceeds 10% annually in many low- and middle-income countries, while it is close to stagnant in high-income countries. Breast-milk substitutes are marketed directly to consumers via mass media and print advertisements and indirectly via incentives, free supplies, and promotions to and through health workers and facilities, retailers, and policy makers. Internet marketing via company web sites and social media is on the rise. Marketing influences social norms by making formula use seem to be extensive, modern, and comparable to or better than breast milk. Clear evidence of a negative impact is found when breast-milk substitutes are provided for free in maternity facilities and when they are promoted by health workers and in the media. Influences through other channels are plausible, but rigorous studies are lacking. It was not possible with the data available to quantify the impact of marketing relative to other factors on suboptimal breastfeeding behaviors. Marketing remains widespread even in countries that have adopted the International Code of Marketing of Breast-milk Substitutes to restrict such activities. Adoption of stricter regulatory frameworks coupled with independent, quantitative monitoring and compliance enforcement are needed to counter the impacts of formula marketing globally. © The Author(s) 2015.

Effect of Substituted Ca on the Thermoelectric and Optoelectronic Properties of NaRh2O4 Under Pressure

NASA Astrophysics Data System (ADS)

Rahnamaye Aliabad, H. A.; Hosseini, N.

2018-03-01

In this paper, we have used the first principle calculations for investigation of the structural, optoelectronic and thermoelectric properties of NaRh2O4 compound and substituted with Ca onto the Na sites under pressure. The results show that there are two direct band gaps for the NaRh2O4 compound and three indirect band gaps for the CaRh2O4 compound at the top of the Fermi level. The size of the band gaps increases almost linearly with the increase of the pressure up to 37 GPa. The calculated density of states for the CaRh2O4 compound show that the Ca-3 p state plays a key role for enhancement of the thermoelectric figure of merit ( ZT). We found that the static dielectric function value decreases along the x, y and z directions for the CaRh2O4 compound with the increase of the pressure while it is constant along the x and y directions for the NaRh2O4 compound. The birefringence properties with metallic nature are achieved from the optical spectra. The thermoelectric results show that the maximum peak of the ZT shifts towards the higher value of temperature for the NaRh2O4 compound. The Ca substitution onto the Na sites in the NaRh2O4 compound enhances the ZT value of 0.79 at 250 K.

Synthesis of 2H- and 13C-substituted dithanes

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2003-01-01

The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

Synthesis Of 2h- And 13c-Substituted Dithanes

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2004-05-04

The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

Multiple Genetic Pathways Involving Amino Acid Position 143 of HIV-1 Integrase Are Preferentially Associated with Specific Secondary Amino Acid Substitutions and Confer Resistance to Raltegravir and Cross-Resistance to Elvitegravir

PubMed Central

Frantzell, Arne; Fransen, Signe; Petropoulos, Christos J.

2013-01-01

Y143C,R substitutions in HIV-1 integrase define one of three primary raltegravir (RAL) resistance pathways. Here we describe clinical isolates with alternative substitutions at position 143 (Y143A, Y143G, Y143H, and Y143S [Y143A,G,H,S]) that emerge less frequently, and we compare the genotypic and phenotypic profiles of these viruses to Y143C,R viruses to reconcile the preferential selection of Y143C,R variants during RAL treatment. Integrase amino acid sequences and RAL susceptibility were characterized in 117 patient isolates submitted for drug resistance testing and contained Y143 amino acid changes. The influence of specific Y143 substitutions on RAL susceptibility and their preferential association with particular secondary substitutions were further defined by evaluating the composition of patient virus populations along with a large panel of site-directed mutants. Our observations demonstrate that the RAL resistance profiles of Y143A,G,H,S viruses and their association with specific secondary substitutions are similar to the well-established Y143C profile but distinct from the Y143R profile. Y143R viruses differ from Y143A,C,G,H,S viruses in that Y143R confers a greater reduction in RAL susceptibility as a single substitution, consistent with a lower resistance barrier. Among Y143A,C,G,H,S viruses, the higher prevalence of Y143C viruses is the result of a lower genetic barrier than that of the Y143A,G,S viruses and a lower resistance barrier than that of the Y143H viruses. In addition, Y143A,C,G,H,S viruses require multiple secondary substitutions to develop large reductions in RAL susceptibility. Patient-derived viruses containing Y143 substitutions exhibit cross-resistance to elvitegravir. PMID:23733474

Aryl substitution of pentacenes

PubMed Central

Waterloo, Andreas R; Sale, Anna-Chiara; Lehnherr, Dan; Hampel, Frank

2014-01-01

Summary A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films), thermoanalytical methods (DSC and TGA), cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives). X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices. PMID:25161729

Metal- and Reagent-Free Anodic C-C Cross-Coupling of Phenols with Benzofurans leading to a Furan Metathesis.

PubMed

Lips, Sebastian; Frontana-Uribe, Bernardo Antonio; Dörr, Maurice; Schollmeyer, Dieter; Franke, Robert; Waldvogel, Siegfried R

2018-04-20

Heterobiaryls consisting of a phenol and a benzofuran motif are of significant importance for pharmaceutical applications. An attractive sustainable, metal- and reagent-free, electrosynthetic, and highly efficient method, that allows access to (2-hydroxyphenyl)benzofurans is presented. Upon the electrochemical dehydrogenative C-C cross-coupling reaction, a metathesis of the benzo moiety at the benzofuran occurs. This gives rise to a substitution pattern at the hydroxyphenyl moiety which would not be compatible by a direct coupling process. The single-step protocol is easy to conduct in an undivided electrolysis cell, therefore scalable, and inherently safe. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simplified, inverse, ejector design tool

NASA Technical Reports Server (NTRS)

Dechant, Lawrence J.

1993-01-01

A simple lumped parameter based inverse design tool has been developed which provides flow path geometry and entrainment estimates subject to operational, acoustic, and design constraints. These constraints are manifested through specification of primary mass flow rate or ejector thrust, fully-mixed exit velocity, and static pressure matching. Fundamentally, integral forms of the conservation equations coupled with the specified design constraints are combined to yield an easily invertible linear system in terms of the flow path cross-sectional areas. Entrainment is computed by back substitution. Initial comparison with experimental and analogous one-dimensional methods show good agreement. Thus, this simple inverse design code provides an analytically based, preliminary design tool with direct application to High Speed Civil Transport (HSCT) design studies.

Medicaid Disproportionate Share and Other Special Financing Programs

PubMed Central

Ku, Leighton; Coughlin, Teresa A.

1995-01-01

Medicaid disproportionate share hospital (DSH) and related programs, such as provider-specific taxes or intergovernmental transfers (IGTs), help support uncompensated care and effectively reduce State Medicaid expenditures by increasing Federal matching funds. We analyze the uses of these funds, based on a survey completed by 39 States and case studies of 6 States. We find that only a small share of these funds were available to cover the costs of uncompensated care. One method to ensure that funds are used for health care would be to reprogram funds into health insurance subsidies. An alternative to improve equity of funding across the Nation would be to create a substitute Federal grant program to directly support uncompensated care. PMID:10142580

Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

PubMed

Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

2017-10-23

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance liquid chromatography study of the enantiomer separation of chrysanthemic acid and its analogous compounds on a terguride-based stationary phase.

PubMed

Dondi, M; Flieger, M; Olsovska, J; Polcaro, C M; Sinibaldi, M

1999-10-29

The direct enantioseparation of chrysanthemic acid [2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid] and its halogen-substituted analogues was systematically studied by HPLC using a terguride-based chiral stationary phase in combination with a UV diode array and chiroptical detectors. Isomers with (1R) configuration always eluted before those with (IS) configuration. The elution sequence of cis- and trans-isomers was strongly affected by mobile phase pH, whereas the enantioselectivity remained the same. Conditions for the separation of all the enantiomers were also examined. This method was used for monitor the hydrolytic degradation products of Cyfluthrin (Baythroid) in soil under laboratory conditions.

Spatially resolved organic analysis of the Allende meteorite

NASA Technical Reports Server (NTRS)

Zenobi, Renato; Philippoz, Jean-Michel; Zare, Richard N.; Buseck, Peter R.

1989-01-01

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende meteorite has been probed with two-step laser desorption/laser multiphoton ionization mass spectrometry. This method allows direct in situ analysis with a spatial resolution of 1 sq mm or better of selected organic molecules. Spectra from freshly fractured interior surfaces of the meteorite show that PAH concentrations are locally high compared to the average concentrations found by wet chemical analysis of pulverized samples. The data suggest that the PAHs are primarily associated with the fine-grained matrix, where the organic polymer occurs. In addition, highly substituted PAH skeletons were observed. Interiors of individual chondrules were devoid of PAHs at the detection limit (about 0.05 ppm).

Research progress on trifluoromethyl-based radical reaction process

NASA Astrophysics Data System (ADS)

Song, Hao

2017-12-01

Due to the unique properties imparted by the trifluoromethyl group, such as high electron density and strong lipotropy, which effectively improve acidity, lipophilicity and metabolic stability of the molecule itself, trifluoromethyl-substituted organic compounds are becoming increasingly important as structural motifs in pharmaceuticals, agrochemicals and organic materials. In this review, we present several methods developed for the direct introduction of a trifluoromethyl group, beginning with its rich and storied history. Then the present article addresses mechanism and process in carbon-carbon bond forming reaction based on radical process which is divided into three parts according to the way of CF3 radical generation. Finally, challenges and opportunities of researches on trifluoromethylation reactions facing are prospected.

Benzoyl radicals from (hetero)aromatic aldehydes. Decatungstate photocatalyzed synthesis of substituted aromatic ketones.

PubMed

Ravelli, Davide; Zema, Michele; Mella, Mariella; Fagnoni, Maurizio; Albini, Angelo

2010-09-21

Benzoyl radicals are generated directly from (hetero)aromatic aldehydes upon tetrabutylammonium decatungstate ((n-Bu(4)N)(4)W(10)O(32)), TBADT) photocatalysis under mild conditions. In the presence of alpha,beta-unsaturated esters, ketones and nitriles radical conjugate addition ensues and gives the corresponding beta-functionalized aryl alkyl ketones in moderate to good yields (stereoselectively in the case of 3-methylene-2-norbornanone). Due to the mild reaction conditions the presence of various functional groups on the aromatic ring is tolerated (e.g. methyl, methoxy, chloro). The method can be applied to hetero-aromatic aldehydes whether electron-rich (e.g. thiophene-2-carbaldehyde) or electron-poor (e.g. pyridine-3-carbaldehyde).

Study of cation magnetic moment directions in Cr (Co) doped nickel ferrites

NASA Astrophysics Data System (ADS)

Lang, L. L.; Xu, J.; Qi, W. H.; Li, Z. Z.; Tang, G. D.; Shang, Z. F.; Zhang, X. Y.; Wu, L. Q.; Xue, L. C.

2014-09-01

Powder samples of the ferrites MxNi1-xFe2O4 (M = Cr, Co and 0.0 ≤ x ≤ 0.3) were prepared using a chemical co-precipitation method. X-ray diffraction analysis showed that the two series of samples had a single-phase cubic spinel structure. It was found that the magnetic moments (μexp) per formula of samples measured at 10 K decreased when Cr substituted for Ni, but increased when Co substituted for Ni, in spite of the fact that the magnetic moments of Cr2+ (4 μB) and Co2+ (3 μB) are higher than that of Ni2+ (2 μB). With the assumption that the magnetic moments of Cr2+ and Cr3+ lie antiparallel to those of the Fe, Co, and Ni cations in the same sublattices of spinel ferrites, the dependences on the Cr (Co) doping level of the sample magnetic moments at 10 K were fitted successfully, using the quantum-mechanical potential barrier model earlier proposed by our group. For the two series of samples, the fitted magnetic moments are close to the experimental results.

Chirality transfer effects in proline-substituted coumarin compounds.

PubMed

Park, Eun-Kyung; Park, Bongjeong; Choi, Jun-Ho; Choi, Kihang; Cho, Minhaeng

2009-08-13

Conformations of proline-substituted chromophores are determined by using circular dichroism (CD) spectroscopy and quantum chemistry calculation method. Coumarin is chosen for the optical chromophore and proline amino acid is attached to its C7 position. The coumarin-proline conjugate considered contains both fluorophore and peptide linker where any polypeptides or biomolecules can be additionally connected to the free carboxyl group of the proline. Thus, the coumarin-proline is a potentially useful composite chirality-probe system for studies of protein dynamics in solution. However, detailed conformation of coumarin ring with respect to the proline ring has to be determined first. We found that there are two possible conformers, which differ from each other by the relative orientation of the coumarin ring. Comparing the measured CD spectra with the calculated ones, we directly show that only one of the two conformers is dominant in polar solvents except for water. The present study suggests that the local structure around an optical chromophore, when it is introduced to polypeptides or other biomolecules, can be studied by examining the electronic optical activity of the probe chromophore, as long as the chirality transfer from the attached amino acid to the chromophore is significantly large.

Growth, Crystal Structure and Magnetic Characterization of Zn-Stabilized CePtIn4

NASA Astrophysics Data System (ADS)

Carnicom, Elizabeth M.; Klimczuk, Tomasz; von Rohr, Fabian; Winiarski, Michal J.; Kong, Tai; Stolze, Karoline; Xie, Weiwei; Kushwaha, Satya K.; Cava, Robert J.

2017-08-01

The growth and characterization of CePtIn4, stabilized by 10% Zn substitution for In, is reported. The new material is orthorhombic, space group Cmcm (No. 63), with lattice parameters a = 4.51751(4) Å, b = 16.7570(2) Å, and c = 7.36682(8) Å, and the refined crystal composition has 10% of Zn substituted for In, i.e., the crystals are CePt(In0.9Zn0.1)4. Crystals were grown using a self-flux method: only growths containing Zn yielded CePtIn4 crystals, while Ce3Pt4In13 crystals formed when Zn was not present. Anisotropic temperature-dependent magnetic susceptibilities for single crystals show that Zn-stabilized CePtIn4 orders magnetically at ˜1.9 K. High-temperature Curie-Weiss fits indicate an effective moment of ˜2.49 μB/Ce and a directionally averaged Weiss-temperature of approximately -31 K. Specific heat data shows a peak consistent with the ordering temperature seen in the magnetic susceptibility data. Zn-stabilized CePtIn4 is metallic and displays no superconducting transition down to 0.14 K.

Characterisation of β-tricalcium phosphate-based bone substitute materials by electron paramagnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Matković, Ivo; Maltar-Strmečki, Nadica; Babić-Ivančić, Vesna; Dutour Sikirić, Maja; Noethig-Laslo, Vesna

2012-10-01

β-TCP based materials are frequently used as dental implants. Due to their resorption in the body and direct contact with tissues, in order to inactivate bacteria, fungal spores and viruses, they are usually sterilized by γ-irradiation. However, the current literature provides little information about effects of the γ-irradiation on the formation and stability of the free radicals in the bone graft materials during and after sterilization procedure. In this work five different bone graft substitution materials, composed of synthetic beta tricalcium phosphate (β-TCP) and hydroxyapatite (HAP) present in the market were characterized by electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Paramagnetic species Mn2+, Fe3+, trapped H-atoms and CO2- radicals were detected in the biphasic material (60% HAP, 40% β-TCP), while in β-TCP materials only Mn2+ andor trapped hydrogen atoms were detected. EPR analysis revealed the details of the structure of these materials at the atomic level. The results have shown that EPR spectroscopy is a method which can be used to improve the quality control of bone graft materials after syntering, processing and sterilization procedure.

Sensory rehabilitation in the plastic brain.

PubMed

Collignon, Olivier; Champoux, François; Voss, Patrice; Lepore, Franco

2011-01-01

The purpose of this review is to consider new sensory rehabilitation avenues in the context of the brain's remarkable ability to reorganize itself following sensory deprivation. Here, deafness and blindness are taken as two illustrative models. Mainly, two promising rehabilitative strategies based on opposing theoretical principles will be considered: sensory substitution and neuroprostheses. Sensory substitution makes use of the remaining intact senses to provide blind or deaf individuals with coded information of the lost sensory system. This technique thus benefits from added neural resources in the processing of the remaining senses resulting from crossmodal plasticity, which is thought to be coupled with behavioral enhancements in the intact senses. On the other hand, neuroprostheses represent an invasive approach aimed at stimulating the deprived sensory system directly in order to restore, at least partially, its functioning. This technique therefore relies on the neuronal integrity of the brain areas normally dedicated to the deprived sense and is rather hindered by the compensatory reorganization observed in the deprived cortex. Here, we stress that our understanding of the neuroplastic changes that occur in sensory-deprived individuals may help guide the design and the implementation of such rehabilitative methods. Copyright © 2011 Elsevier B.V. All rights reserved.

Quantitative autoradiographic mapping of focal herpes simplex virus encephalitis using a radiolabeled antiviral drug

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

Price, R.

1984-12-18

A method of mapping herpes simplex viral infection comprising administering a radiolabeled antiviral active 5-substituted 1-(2'-deoxy-2'-substituted-D-arabinofuranosyl) pyrimidine nucleoside to the infected subject, and scanning the area in which the infection is to be mapped for the radiolabel.

Synthesis of densely substituted trans-configured 4-acylated piperidine-2,4-diones as 3:1 adducts of imines and ketenes.

PubMed

Cabrera, José; Hellmuth, Tina; Peters, René

2010-06-18

An operationally simple method is described to form densely substituted diastereomerically pure trans-configured and potentially biologically interesting 5,6-dihydropyridone derivatives as 3:1 adducts of ketenes formed in situ from acyl bromides and aromatic imines.

THE DEVELOPMENT AND APPLICATION OF AN IC-ICP-MS METHOD FOR THE SPECIATION OF METHYLTINS.

EPA Science Inventory

The determination of organotin compounds in environmental samples is of concern as the species have varying degrees of toxicity. Generally, the most toxic organotin compounds belong to the tri alkyl substituted variety followed by the di- and mono-substituted organotins. The low...

Blob-enhanced reconstruction technique

NASA Astrophysics Data System (ADS)

Castrillo, Giusy; Cafiero, Gioacchino; Discetti, Stefano; Astarita, Tommaso

2016-09-01

A method to enhance the quality of the tomographic reconstruction and, consequently, the 3D velocity measurement accuracy, is presented. The technique is based on integrating information on the objects to be reconstructed within the algebraic reconstruction process. A first guess intensity distribution is produced with a standard algebraic method, then the distribution is rebuilt as a sum of Gaussian blobs, based on location, intensity and size of agglomerates of light intensity surrounding local maxima. The blobs substitution regularizes the particle shape allowing a reduction of the particles discretization errors and of their elongation in the depth direction. The performances of the blob-enhanced reconstruction technique (BERT) are assessed with a 3D synthetic experiment. The results have been compared with those obtained by applying the standard camera simultaneous multiplicative reconstruction technique (CSMART) to the same volume. Several blob-enhanced reconstruction processes, both substituting the blobs at the end of the CSMART algorithm and during the iterations (i.e. using the blob-enhanced reconstruction as predictor for the following iterations), have been tested. The results confirm the enhancement in the velocity measurements accuracy, demonstrating a reduction of the bias error due to the ghost particles. The improvement is more remarkable at the largest tested seeding densities. Additionally, using the blobs distributions as a predictor enables further improvement of the convergence of the reconstruction algorithm, with the improvement being more considerable when substituting the blobs more than once during the process. The BERT process is also applied to multi resolution (MR) CSMART reconstructions, permitting simultaneously to achieve remarkable improvements in the flow field measurements and to benefit from the reduction in computational time due to the MR approach. Finally, BERT is also tested on experimental data, obtaining an increase of the signal-to-noise ratio in the reconstructed flow field and a higher value of the correlation factor in the velocity measurements with respect to the volume to which the particles are not replaced.

Effects of Vanadium Substitution on the Structure and Photocatalytic Behavior of ETS-10

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

Shough,A.; Doren, D.; Nash, M.

2007-01-01

A combination of experimental and computational methods has been used to investigate the effects of vanadium doping in ETS-10. Near edge X-ray absorption fine structure (NEXAFS) spectra reveal octahedrally coordinated V{sup IV} and V{sup V} species within V-doped ETS-10 materials, confirming substitution for Ti{sup IV} sites only. Computational models, using hybrid density functional theory/molecular mechanics (DFT/MM) methods, have been developed that contain varying concentrations of V{sup IV} and V{sup V} within the O-M-O (M = Ti, V) chain. Geometry optimizations indicate that V{sup V} substitution leads to larger changes in the local chain geometry than V{sup IV} substitution. Substitution energeticsmore » for V{sup IV} and V{sup V} in different sites have been calculated to determine preferred locations of the two species, suggesting that long chains of V{sup V} are not stable and demonstrating the need for both V{sup V} and V{sup IV} within V-substituted materials. Wavefunctions for systems with an electron added or removed are used to identify electron and hole trapping sites associated with the V{sup V} and V{sup IV} doping centers respectively. An increase in photocatalytic activity is predicted at low [V] due to improved charge separation. However photocatalytic activity is expected to decrease at high [V] due to increased carrier recombination. These results are consistent with recent experimental data.« less

Successful tactile based visual sensory substitution use functions independently of visual pathway integrity

PubMed Central

Lee, Vincent K.; Nau, Amy C.; Laymon, Charles; Chan, Kevin C.; Rosario, Bedda L.; Fisher, Chris

2014-01-01

Purpose: Neuronal reorganization after blindness is of critical interest because it has implications for the rational prescription of artificial vision devices. The purpose of this study was to distinguish the microstructural differences between perinatally blind (PB), acquired blind (AB), and normally sighted controls (SCs) and relate these differences to performance on functional tasks using a sensory substitution device (BrainPort). Methods: We enrolled 52 subjects (PB n = 11; AB n = 35; SC n = 6). All subjects spent 15 h undergoing BrainPort device training. Outcomes of light perception, motion, direction, temporal resolution, grating, and acuity were tested at baseline and after training. Twenty-six of the subjects were scanned with a three Tesla MRI scanner for diffusion tensor imaging (DTI), and with a positron emission tomography (PET) scanner for mapping regional brain glucose consumption during sensory substitution function. Non-parametric models were used to analyze fractional anisotropy (FA; a DTI measure of microstructural integrity) of the brain via region-of-interest (ROI) analysis and tract-based spatial statistics (TBSS). Results: At baseline, all subjects performed all tasks at chance level. After training, light perception, time resolution, location and grating acuity tasks improved significantly for all subject groups. ROI and TBSS analyses of FA maps show areas of statistically significant differences (p ≤ 0.025) in the bilateral optic radiations and some visual association connections between all three groups. No relationship was found between FA and functional performance with the BrainPort. Discussion: All subjects showed performance improvements using the BrainPort irrespective of nature and duration of blindness. Definite brain areas with significant microstructural integrity changes exist among PB, AB, and NC, and these variations are most pronounced in the visual pathways. However, the use of sensory substitution devices is feasible irrespective of microstructural integrity of the primary visual pathways between the eye and the brain. Therefore, tongue based devices devices may be usable for a broad array of non-sighted patients. PMID:24860473

The hospital nursing shortage. A paradox of increasing supply and increasing vacancy rates.

PubMed Central

Aiken, L H

1989-01-01

A serious shortage of nurses has developed since 1984 despite a growing number of employed nurses and a substantial decline in the number of hospital inpatient days. The evidence suggests that the shortage is the result of an increased demand for nurses, not a decline in supply. The increased demand in large part has resulted from the substitution of registered nurses for licensed practical nurses, aides, and other patient services personnel. The substitution was feasible because nurses' wages have been depressed compared with those of other hospital employees. The shortage is likely to abate if nurses' wages increase, making substitution more costly. Even in the absence of continuing wage increases, hospitals could ease the shortage by restructuring patient services and enabling nurses to spend a greater portion of their time in direct patient care. PMID:2669349

In vitro culture of large bone substitutes in a new bioreactor: importance of the flow direction.

PubMed

Olivier, V; Hivart, Ph; Descamps, M; Hardouin, P

2007-09-01

New biomaterials combined with osteogenic cells are now being developed as an alternative to autogeneous bone grafts when the skeletal defect reaches a critical size. Yet, the size issue appears to be a key obstacle in the development of bone tissue engineering. Bioreactors are needed to allow the in vitro expansion of cells inside large bulk materials under appropriate conditions. However, no bioreactor has yet been designed for large-scale 3D structures and custom-made scaffolds. In this study, we evaluate the efficiency of a new bioreactor for the in vitro development of large bone substitutes, ensuring the perfusion of large ceramic scaffolds by the nutritive medium. The survival and proliferation of cells inside the scaffolds after 7 and 28 days in this dynamic culture system and the impact of the direction of the flow circulation are evaluated. The follow-up of glucose consumption, DNA quantification and microscopic evaluation all confirmed cell survival and proliferation for a sample under dynamic culture conditions, whereas static culture leads to the death of cells inside the scaffolds. Two directions of flow perfusion were assayed; the convergent direction leads to enhanced results compared to divergent flow.

The review of various synthesis methods of barium titanate with the enhanced dielectric properties

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

More, S. P., E-mail: smitalomte@gmail.com; Topare, R. J., E-mail: r-topare@yahoo.com

2016-05-06

The Barium Titanate is a very well known dielectric ceramic belongs to perovskite structure. It has very wide applications in the field of electronic, electro ceramic, electromechanical and electro-optical applications. Barium Titanate has very high dielectric constant as well as low dielectric loss. Substituted dielectrics are one of the most important technological compounds in modern electro ceramics. Its electrical properties can be tuned flexibly by a simple substitution technique. This has encouraged researchers to select a typical cation to be substituted at cationic sites. In the present paper, the review of various synthesis methods of Barium Titanate compound with themore » effect of different dopants, the grain size on the dielectric properties at various temperatures is discussed.« less

Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

PubMed

Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

2013-12-02

A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laccase-catalyzed α-arylation of benzoylacetonitrile with substituted hydroquinones

DOE PAGES

Cannatelli, Mark D.; Ragauskas, Arthur J.

2014-09-03

This article investigates a green method for α-arylation of a primary nitrile. Compounds possessing a benzylic nitrile have shown to exhibit biological activity. Laccases (benzenediol:oxygen oxidoreductase EC 1.10.3.2) were used as the catalysts to perform the cross-coupling reaction between benzoylacetonitrile and substituted hydroquinones. The corresponding 2-substituted 3-oxo-3-phenylpropanenitriles where synthesized in moderate to excellent yields in pH 7.0 buffered water under mild conditions. The substituent on the hydroquinone had a significant impact on product yields and regioselectivity of reaction. The use of laccases, which require O 2 as their only co-substrate and produce H 2O as their only by-product, to performmore » this transformation is an environmentally benign method for α-arylation of primary nitriles.« less

Theoretical investigations of the thermochemistry, structures, and internal rotation of conjugated polyynes

NASA Astrophysics Data System (ADS)

Jarowski, Peter D.

Chapter 1 discusses the thermochemistry of conjugated double and triple bonds. The conjugation stabilization energies of dienes and diynes are considerably larger than estimates based on heat of hydrogenation differences between 1,3-butadiyne and 1-butyne as well as between 1,3-butadiene and 1-butene. Such comparisons do not take into account the counterbalancing hyperconjugative stabilization of the partially hydrogenated products by their ethyl groups. When alkyl hyperconjugation is considered, the conjugation stabilization of diynes (≈ 9.3 kcal/mol) is found by two methods (involving isomerization of non-conjugated into conjugated isomers and heats of hydrogenation) to be larger than that of dienes (≈ 8.2 kcal/mol). In Chapter 2 the stabilization of substituted organic radicals, relative to methyl, are computed using bond separation energies and the block localized wavefunction method. These energies are typically evaluated from C-H bond dissociation energies (computed here by the CBS-RAD method). However, this method gives stabilization energies of an increasing number of mono-, di-, and tri-substituted vinyl and ethynyl substituents, which differ from the predictions of Perturbation Molecular Orbital (PMO) and Huckel Molecular Orbital (HMO) theory. The saturation (attenuation) effect for both series should be monotonic and small. Instead, the attenuation computed by the allylic series is larger than that predicted by HMO theory and the behavior of the propargylic series is erratic. These discrepancies arise from the use of bond dissociation energy data in the evaluations, which depend not only on the stabilization of the radicals, but also on the substantial substituent effects (e.g., hyperconjugation) on the energies of the reference hydrocarbons. New evaluation schemes are proposed that avoid such complications and thus estimate radical stabilization effects directly; the results agree with PMO and HMO theories. Substitution effects are analyzed using isodesmic equations with CBS-RAD data and also with the block localized wavefunction (BLW) method. The new estimates give essentially the same vinyl (22.3 kcal/mol) and ethynyl (21.9 kcal/mol) stabilization energies in the allyl and propargyl radicals, contrary to conventional evaluations. Likewise, the vinyl and ethynyl stabilizations in di-substituted and tri-substituted radicals are similar. These conclusions are corroborated with the block localized wavefunction (BLW) method, which is used to analyze resonance stabilization energies in the radical systems and hyperconjugative stabilization energies in the reference hydrocarbons. Chapter 3 presents the structures, heats of formation, and strain energies of diacetylene (buta-1,3-diynediyl) expanded molecules computed with ab initio and molecular mechanics calculations. Expanded cubane, prismane, tetrahedrane, and expanded monocyclics and bicyclics were optimized at the HF/6-31G(d) and B3LYP/6-31G(d) levels. The heats of formation of these systems were obtained from isodesmic equations at the HF/6-31G(d) level. Heats of formation were also calculated from Benson group equivalents. The strain energies of these expanded molecules were estimated by several independent methods. An adapted MM3* molecular mechanics force field, specifically parameterized to treat conjugated acetylene units, was employed for one measure of strain energy and as an additional method for structural analysis. Expanded dodecahedrane and icosahedrane were calculated by this method. Expanded molecules were considered structurally in the context of their potential material applications. Chapter 4 addresses the computation of the rotational barriers of substituted ethynlene and butatriene as well as their geometric and electronic structures. The barriers to internal rotation of methylated, ethynylated, and vinylated butatrienes and alkenes were calculated at the CASPT2/6-31G(d)//B3LYP/6-31G(d) level. Calculated butatriene rotational barriers are lower than analogous alkenes, but there is a larger variance in rotational barrier for alkenes than for butatrienes. The barriers to rotation were analyzed by isodesmic equations designed to estimate the substituent effects in the ground (GS) and transition state (TS) individually. The GSs of both series are stabilized to roughly the same extent. In contrast, the TSs of butatrienes are more stabilized overall than those of alkenes. Much of the stabilization in the TS of butatrienes comes from the internal triple bond and not from the substituent. Estimation of the substituent stabilization alone reveals the TSs of ethylenes to be more stabilized by substitution than butatrienes. In Chapter 5 the energetic and structural changes taking place upon rotation of the central phenylene of 1,4-bis(3,3,3-triphenylpropynyl)benzene molecular gyroscopes in the solid-state were computed using molecular mechanics calculations. Pseudopolymorphic crystals of a benzene clathrate (1A) and a desolvated form (1B) were analyzed with models that account for varying degrees of freedom within the corresponding lattices. The calculated rotational barriers in a rigid lattice approximation, 78 kcal/mol for 1A and 72 kcal/mol for 1B, are about five times greater than those previously measured by variable temperature 13C CPMAS NMR and quadrupolar echo 2H NMR line shape analysis; 12.8 kcal/mol for 1A and 14.6 kcal/mol for 1B. The rotational barriers calculated with a model that restricts whole body rotation and translational motions but allows for internal rotations give results that are consistent with experiment. The calculated barriers for 1A and 1B are 15.5 kcal/mol and 16.2 kcal/mol, respectively. The differences between the two models are attributed to the effect of correlated motions of the lattice and the rotating group, which are evident from the structural analysis of the atomic position data as a function of the dihedral angle of the rotator. The displacements of neighboring molecules near the rotary transition states for 1A and 1B can be as large as 2.7 and 1.1 A, respectively. While the displacement of interpenetrating phenyl rings from neighboring rotors proximal to the event are significant for both 1A and 1B, six-fold (C6) benzene rotations in clathrate 1A were found to be directly correlated to the rotation the phenylene rotator. The Trueblood model estimates solid-state rotational barriers by fitting anisotropic displacement parameters (thermal ellipsoids) from X-ray diffraction data determined at varying temperature to quadratic or sinusoidal functions that approximate the potential energy profile to libration. The applicability of this model towards substituted and unsubstituted 1,4-bis(3,3,3-triphenylpropynyl)benzene molecular rotor crystals is gauged using computational data generated from molecular mechanics force field calculations. Unsubstituted and mono-fluoro, -amino, and -nitro, substituted derivatives are calculated. Benzene clathrate polymorphs are also included. Estimated barriers agree well with experimental data, although they are slightly overestimated. The barriers are not strictly correlated to substituent volume and reside within a small range of values.

An insight into the dopant selection for CeO2-based resistive-switching memory system: a DFT and experimental study

NASA Astrophysics Data System (ADS)

Hussain, Fayyaz; Imran, Muhammad; Rana, Anwar Manzoor; Khalil, R. M. Arif; Khera, Ejaz Ahmad; Kiran, Saira; Javid, M. Arshad; Sattar, M. Atif; Ismail, Muhammad

2018-03-01

The aim of this study is to figure out better metal dopants for CeO2 for designing highly efficient non-volatile memory (NVM) devices. The present DFT work involves four different metals doped interstitially and substitutionally in CeO2 thin films. First principle calculations involve electron density of states (DOS) and partial density of states (PDOS), and isosurface charge densities are carried out within the plane-wave density functional theory using GGA and GGA + U approach by employing the Vienna ab initio simulation package VASP. Isosurface charge density plots confirmed that interstitial doping of Zr and Ti metals truly assists in generating conduction filaments (CFs), while substitutional doping of these metals cannot do so. Substitutional doping of W may contribute in generating CFs in CeO2 directly, but its interstitial doping improves conductivity of CeO2. However, Ni-dopant is capable of directly generating CFs both as substitutional and interstitial dopants in ceria. Such a capability of Ni appears acting as top electrode in Ni/CeO2/Pt memory devices, but its RS behavior is not so good. On inserting Zr layer to make Ni/Zr:CeO2/Pt memory stacks, Ni does not contribute in RS characteristics, but Zr plays a vital role in forming CFs by creating oxygen vacancies and forming ZrO2 interfacial layer. Therefore, Zr-doped devices exhibit high-resistance ratio of 104 and good endurance as compared to undoped devices suitable for RRAM applications.

Semirational Directed Evolution of Loop Regions in Aspergillus japonicus β-Fructofuranosidase for Improved Fructooligosaccharide Production

PubMed Central

Trollope, K. M.; Görgens, J. F.

2015-01-01

The Aspergillus japonicus β-fructofuranosidase catalyzes the industrially important biotransformation of sucrose to fructooligosaccharides. Operating at high substrate loading and temperatures between 50 and 60°C, the enzyme activity is negatively influenced by glucose product inhibition and thermal instability. To address these limitations, the solvent-exposed loop regions of the β-fructofuranosidase were engineered using a combined crystal structure- and evolutionary-guided approach. This semirational approach yielded a functionally enriched first-round library of 36 single-amino-acid-substitution variants with 58% retaining activity, and of these, 71% displayed improved activities compared to the parent. The substitutions yielding the five most improved variants subsequently were exhaustively combined and evaluated. A four-substitution combination variant was identified as the most improved and reduced the time to completion of an efficient industrial-like reaction by 22%. Characterization of the top five combination variants by isothermal denaturation assays indicated that these variants displayed improved thermostability, with the most thermostable variant displaying a 5.7°C increased melting temperature. The variants displayed uniquely altered, concentration-dependent substrate and product binding as determined by differential scanning fluorimetry. The altered catalytic activity was evidenced by increased specific activities of all five variants, with the most improved variant doubling that of the parent. Variant homology modeling and computational analyses were used to rationalize the effects of amino acid changes lacking direct interaction with substrates. Data indicated that targeting substitutions to loop regions resulted in improved enzyme thermostability, specific activity, and relief from product inhibition. PMID:26253664

Direct Biotransformation of Dioscin into Diosgenin in Rhizome of Dioscorea zingiberensis by Penicillium dioscin.

PubMed

Dong, Jingzhou; Lei, Can; Lu, Dayan; Wang, Ying

2015-06-01

Diosgenin is an important precursor for synthesis of more than 200 steroidal hormone medicines. Rhizome of Dioscorea zingiberensis C. H. Wright (RDZ) contained the highest content of diosgenin in Dioscorea plant species. Diosgenin is traditionally extracted by acid hydrolysis from RDZ. However, the acid hydrolysis process produces massive wastewater which caused serious environment pollution. In this study, diosgenin extraction by direct biotransformation with Penicillium dioscin was investigated. The spawn cultivation conditions were optimized as: Czapeks liquid culture medium without sugar and agar (1,000 ml) + 6.0 g dioscin/6.0 g DL, 30 °C, 36 h; solid fermentation of RDZ: mycelia/RDZ of 0.05 g/kg, 30 °C, 50 h; the yield of diosgenin was over 90 %. Spawn cultivation was crucial for the direct biotransformation. In the spawn cultivation, amount and ratio of dioscin/DL were the key factors to promote biotransformation activity of P. dioscin. This biotransformation method was environment-friendly, simple and energy saving, and might be a potential substitute for acid hydrolysis in diosgenin extraction industry.

A Dicobalt Complex with an Unsymmetrical Quinonoid Bridge Isolated in Three Units of Charge: A Combined Structural, (Spectro)electrochemical, Magnetic and Spectroscopic Study.

PubMed

van der Meer, Margarethe; Rechkemmer, Yvonne; Frank, Uta; Breitgoff, Frauke D; Hohloch, Stephan; Su, Cheng-Yong; Neugebauer, Petr; Marx, Raphael; Dörfel, María; van Slageren, Joris; Sarkar, Biprajit

2016-09-19

Quinonoid ligands are excellent bridges for generating redox-rich dinuclear assemblies. A large majority of these bridges are symmetrically substituted, with examples of unsymmetrically substituted quinonoid bridges being extremely rare. We present here a dicobalt complex in its various redox states with an unsymmetrically substituted quinonoid bridging ligand. Two homovalent forms and one mixed-valent form have been isolated and characterized by single crystal X-ray diffraction. The complex displays a large comproportionation constant for the mixed-valent state which is three orders of magnitude higher than that observed for the analogous complex with a symmetrically substituted bridge. Results from electrochemistry, UV/Vis/NIR spectroelectrochemistry, SQUID magnetometry, multi-frequency EPR spectroscopy and FIR spectroscopy are used to probe the electronic structures of these complexes. FIR provides direct evidence of exchange coupling. The results presented here display the advantages of using an unsymmetrically substituted bridge: site specific redox chemistry, high thermodynamic stabilization of the mixed-valent form, isolation and crystallization of various redox forms of the complex. This work represents an important step on the way to generating heterodinuclear complexes for use in cooperative catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced electronic and magnetic properties by functionalization of monolayer GaS via substitutional doping and adsorption

NASA Astrophysics Data System (ADS)

Rahman, Altaf Ur; Rahman, Gul; Kratzer, Peter

2018-05-01

The structural, electronic, and magnetic properties of two-dimensional (2D) GaS are investigated using density functional theory (DFT). After confirming that the pristine 2D GaS is a non-magnetic, indirect band gap semiconductor, we consider N and F as substitutional dopants or adsorbed atoms. Except for N substituting for Ga (NGa), all considered cases are found to possess a magnetic moment. Fluorine, both in its atomic and molecular form, undergoes a highly exothermic reaction with GaS. Its site preference (FS or FGa) as substitutional dopant depends on Ga-rich or S-rich conditions. Both for FGa and F adsorption at the Ga site, a strong F–Ga bond is formed, resulting in broken bonds within the GaS monolayer. As a result, FGa induces p-type conductivity in GaS, whereas FS induces a dispersive, partly occupied impurity band about 0.5 e below the conduction band edge of GaS. Substitutional doping with N at both the S and the Ga site is exothermic when using N atoms, whereas only the more favourable site under the prevailing conditions can be accessed by the less reactive N2 molecules. While NGa induces a deep level occupied by one electron at 0.5 eV above the valence band, non-magnetic NS impurities in sufficiently high concentrations modify the band structure such that a direct transition between N-induced states becomes possible. This effect can be exploited to render monolayer GaS a direct-band gap semiconductor for optoelectronic applications. Moreover, functionalization by N or F adsorption on GaS leads to in-gap states with characteristic transition energies that can be used to tune light absorption and emission. These results suggest that GaS is a good candidate for design and construction of 2D optoelectronic and spintronics devices.

Enhanced electronic and magnetic properties by functionalization of monolayer GaS via substitutional doping and adsorption.

PubMed

Ur Rahman, Altaf; Rahman, Gul; Kratzer, Peter

2018-05-16

The structural, electronic, and magnetic properties of two-dimensional (2D) GaS are investigated using density functional theory (DFT). After confirming that the pristine 2D GaS is a non-magnetic, indirect band gap semiconductor, we consider N and F as substitutional dopants or adsorbed atoms. Except for N substituting for Ga (N Ga ), all considered cases are found to possess a magnetic moment. Fluorine, both in its atomic and molecular form, undergoes a highly exothermic reaction with GaS. Its site preference (F S or F Ga ) as substitutional dopant depends on Ga-rich or S-rich conditions. Both for F Ga and F adsorption at the Ga site, a strong F-Ga bond is formed, resulting in broken bonds within the GaS monolayer. As a result, F Ga induces p-type conductivity in GaS, whereas F S induces a dispersive, partly occupied impurity band about 0.5 e below the conduction band edge of GaS. Substitutional doping with N at both the S and the Ga site is exothermic when using N atoms, whereas only the more favourable site under the prevailing conditions can be accessed by the less reactive N 2 molecules. While N Ga induces a deep level occupied by one electron at 0.5 eV above the valence band, non-magnetic N S impurities in sufficiently high concentrations modify the band structure such that a direct transition between N-induced states becomes possible. This effect can be exploited to render monolayer GaS a direct-band gap semiconductor for optoelectronic applications. Moreover, functionalization by N or F adsorption on GaS leads to in-gap states with characteristic transition energies that can be used to tune light absorption and emission. These results suggest that GaS is a good candidate for design and construction of 2D optoelectronic and spintronics devices.

Switches in Genomic GC Content Drive Shifts of Optimal Codons under Sustained Selection on Synonymous Sites

PubMed Central

Sun, Yu; Tamarit, Daniel

2017-01-01

Abstract The major codon preference model suggests that codons read by tRNAs in high concentrations are preferentially utilized in highly expressed genes. However, the identity of the optimal codons differs between species although the forces driving such changes are poorly understood. We suggest that these questions can be tackled by placing codon usage studies in a phylogenetic framework and that bacterial genomes with extreme nucleotide composition biases provide informative model systems. Switches in the background substitution biases from GC to AT have occurred in Gardnerella vaginalis (GC = 32%), and from AT to GC in Lactobacillus delbrueckii (GC = 62%) and Lactobacillus fermentum (GC = 63%). We show that despite the large effects on codon usage patterns by these switches, all three species evolve under selection on synonymous sites. In G. vaginalis, the dramatic codon frequency changes coincide with shifts of optimal codons. In contrast, the optimal codons have not shifted in the two Lactobacillus genomes despite an increased fraction of GC-ending codons. We suggest that all three species are in different phases of an on-going shift of optimal codons, and attribute the difference to a stronger background substitution bias and/or longer time since the switch in G. vaginalis. We show that comparative and correlative methods for optimal codon identification yield conflicting results for genomes in flux and discuss possible reasons for the mispredictions. We conclude that switches in the direction of the background substitution biases can drive major shifts in codon preference patterns even under sustained selection on synonymous codon sites. PMID:27540085

Influence of La3+ Substitution on Structure, Morphology and Magnetic Properties of Nanocrystalline Ni-Zn Ferrite

PubMed Central

Dasan, Y. K.; Guan, B. H.; Zahari, M. H.; Chuan, L. K.

2017-01-01

Lanthanum substituted Ni-Zn ferrite nanoparticles (Ni0.5Zn0.5LaxFe1-xO4; 0.00 ≤x≤ 1.00) synthesized by sol-gel method were presented. X-ray diffraction patterns reveal the typical single phase spinel cubic ferrite structure, with the traces of secondary phase for lanthanum substituted nanocrystals. In addition, the structural analysis also demonstrates that the average crystallite size varied in the range of 21–25 nm. FTIR spectra present the two prominent absorption bands in the range of 400 to 600 cm-1 which are the fingerprint region of all ferrites. Surface morphology of both substituted and unsubstituted Ni-Zn ferrite nanoparticle samples was studied using FESEM technique and it indicates a significant increase in the size of spherical shaped particles with La3+ substitution. Magnetic properties of all samples were analyzed using vibrating sample magnetometer (VSM). The results revealed that saturation magnetization (Ms) and coercivity (Hc) of La3+ substituted samples has decreased as compared to the Ni-Zn ferrite samples. Hence, the observed results affirm that the lanthanum ion substitution has greatly influenced the structural, morphology and magnetic properties of Ni-Zn ferrite nanoparticles. PMID:28081257

Influence of La3+ Substitution on Structure, Morphology and Magnetic Properties of Nanocrystalline Ni-Zn Ferrite.

PubMed

Dasan, Y K; Guan, B H; Zahari, M H; Chuan, L K

2017-01-01

Lanthanum substituted Ni-Zn ferrite nanoparticles (Ni0.5Zn0.5LaxFe1-xO4; 0.00 ≤x≤ 1.00) synthesized by sol-gel method were presented. X-ray diffraction patterns reveal the typical single phase spinel cubic ferrite structure, with the traces of secondary phase for lanthanum substituted nanocrystals. In addition, the structural analysis also demonstrates that the average crystallite size varied in the range of 21-25 nm. FTIR spectra present the two prominent absorption bands in the range of 400 to 600 cm-1 which are the fingerprint region of all ferrites. Surface morphology of both substituted and unsubstituted Ni-Zn ferrite nanoparticle samples was studied using FESEM technique and it indicates a significant increase in the size of spherical shaped particles with La3+ substitution. Magnetic properties of all samples were analyzed using vibrating sample magnetometer (VSM). The results revealed that saturation magnetization (Ms) and coercivity (Hc) of La3+ substituted samples has decreased as compared to the Ni-Zn ferrite samples. Hence, the observed results affirm that the lanthanum ion substitution has greatly influenced the structural, morphology and magnetic properties of Ni-Zn ferrite nanoparticles.

Magnesium- and strontium-co-substituted hydroxyapatite: the effects of doped-ions on the structure and chemico-physical properties.

PubMed

Aina, Valentina; Lusvardi, Gigliola; Annaz, Basil; Gibson, Iain R; Imrie, Flora E; Malavasi, Gianluca; Menabue, Ledi; Cerrato, Giuseppina; Martra, Gianmario

2012-12-01

The present study is aimed at investigating the contribution of two biologically important cations, Mg(2+) and Sr(2+), when substituted into the structure of hydroxyapatite (Ca(10)(PO(4))(6)(OH)(2),HA). The substituted samples were synthesized by an aqueous precipitation method that involved the addition of Mg(2+)- and Sr(2+)-containing precursors to partially replace Ca(2+) ions in the apatite structure. Eight substituted HA samples with different concentrations of single (only Mg(2+)) or combined (Mg(2+) and Sr(2+)) substitution of cations have been investigated and the results compared with those of pure HA. The obtained materials were characterized by X-ray powder diffraction, specific surface area and porosity measurements (N(2) adsorption at 77 K), FT-IR and Raman spectroscopies and scanning electron microscopy. The results indicate that the co-substitution gives rise to the formation of HA and β-TCP structure types, with a variation of their cell parameters and of the crystallinity degree of HA with varying levels of substitution. An evaluation of the amount of substituents allows us to design and prepare BCP composite materials with a desired HA/β-TCP ratio.

The association of substituting carbohydrates with total fat and different types of fatty acids with mortality and weight change among diabetes patients.

PubMed

Campmans-Kuijpers, Marjo J; Sluijs, Ivonne; Nöthlings, Ute; Freisling, Heinz; Overvad, Kim; Boeing, Heiner; Masala, Giovanna; Panico, Salvatore; Tumino, Rosario; Sieri, Sabina; Johansson, Ingegerd; Winkvist, Anna; Katzke, Verena A; Kuehn, Tilman; Nilsson, Peter M; Halkjær, Jytte; Tjønneland, Anne; Spijkerman, Annemieke M; Arriola, Larraitz; Sacerdote, Carlotta; Barricarte, Aurelio; May, Anne M; Beulens, Joline W

2016-10-01

Substitution of carbohydrates with fat in a diet for type 2 diabetes patients is still debated. This study aimed to investigate the association between dietary carbohydrate intake and isocaloric substitution with (i) total fat, (ii) saturated fatty acids (SFA), (iii) mono-unsaturated fatty acids (MUFA) and (iv) poly-unsaturated fatty acids (PUFA) with all-cause and cardiovascular (CVD) mortality risk and 5-year weight change in patients with type 2 diabetes. The study included 6192 patients with type 2 diabetes from 15 cohorts of the European Prospective Investigation into Cancer and Nutrition (EPIC). Dietary intake was assessed at recruitment with country-specific food-frequency questionnaires. Cox and linear regression were used to estimate the associations with (CVD) mortality and weight change, adjusting for confounders and using different methods to adjust for energy intake. After a mean follow-up of 9.2 y ± SD 2.3 y, 791 (13%) participants had died, of which 268 (4%) due to CVD. Substituting 10 g or 5 energy% of carbohydrates by total fat was associated with a higher all-cause mortality risk (HR 1.07 [1.02-1.13]), or SFAs (HR 1.25 [1.11-1.40]) and a lower risk when replaced by MUFAs (HR 0.89 [0.77-1.02]). When carbohydrates were substituted with SFAs (HR 1.22 [1.00-1.49]) or PUFAs (HR 1.29 [1.02-1.63]) CVD mortality risk increased. The 5-year weight was lower when carbohydrates were substituted with total fat or MUFAs. These results were consistent over different energy adjustment methods. In diabetes patients, substitution of carbohydrates with SFAs was associated with a higher (CVD) mortality risk and substitution by total fat was associated with a higher all-cause mortality risk. Substitution of carbohydrates with MUFAs may be associated with lower mortality risk and weight reduction. Instead of promoting replacement of carbohydrates by total fat, dietary guideline should continue focusing on replacement by fat-subtypes; especially SFAs by MUFAs. Copyright © 2015 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

DOEpatents

Alvarez, Marc A.; Martinez, Rodolfo A.; Unkefer, Clifford J.

2010-02-16

The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group.

A graph decomposition-based approach for water distribution network optimization

NASA Astrophysics Data System (ADS)

Zheng, Feifei; Simpson, Angus R.; Zecchin, Aaron C.; Deuerlein, Jochen W.

2013-04-01

A novel optimization approach for water distribution network design is proposed in this paper. Using graph theory algorithms, a full water network is first decomposed into different subnetworks based on the connectivity of the network's components. The original whole network is simplified to a directed augmented tree, in which the subnetworks are substituted by augmented nodes and directed links are created to connect them. Differential evolution (DE) is then employed to optimize each subnetwork based on the sequence specified by the assigned directed links in the augmented tree. Rather than optimizing the original network as a whole, the subnetworks are sequentially optimized by the DE algorithm. A solution choice table is established for each subnetwork (except for the subnetwork that includes a supply node) and the optimal solution of the original whole network is finally obtained by use of the solution choice tables. Furthermore, a preconditioning algorithm is applied to the subnetworks to produce an approximately optimal solution for the original whole network. This solution specifies promising regions for the final optimization algorithm to further optimize the subnetworks. Five water network case studies are used to demonstrate the effectiveness of the proposed optimization method. A standard DE algorithm (SDE) and a genetic algorithm (GA) are applied to each case study without network decomposition to enable a comparison with the proposed method. The results show that the proposed method consistently outperforms the SDE and GA (both with tuned parameters) in terms of both the solution quality and efficiency.

Method of solubilizing phthalocyanines and metallophthalocyanines

DOEpatents

Rathke, Jerome W.; Chen, Michael J.; Fendrick, Carol M.

1997-11-04

A one-step method of manufacturing soluble phthalocyanines and metallophthalocyanines, like zinc phthalocyanine, by converting a phthalocyanine or a metallophthalocyanine to a trialkylsilyl-substituted derivative is disclosed. The phthalocyanine or metallophthalocyanine is converted to a soluble trialkylsilyl-substituted derivative by interacting the phthalocyanine or metallophthalocyanine with an active metal amide, like lithium 2,2,6,6-tetramethylpiperidide, and a halotrialkylsilane, like chlorotrimethylsilane, to provide a phthalocyanine compound, like phthalocyanine monomers, dimers or polymers, metalated or unmetalated, that are soluble in organic media.

Method of solubilizing phthalocyanines and metallophthalocyanines

DOEpatents

Rathke, Jerome W.; Chen, Michael J.; Fendrick, Carol M.

1997-01-01

A one-step method of manufacturing soluble phthalocyanines and metallophthalocyanines, like zinc phthalocyanine, by converting a phthalocyanine or a metallophthalocyanine to a trialkylsilyl-substituted derivative is disclosed. The phthalocyanine or metallophthalocyanine is converted to a soluble trialkylsilyl-substituted derivative by interacting the phthalocyanine or metallophthalocyanine with an active metal amide, like lithium 2,2,6,6-tetramethylpiperidide, and a halotrialkylsilane, like chlorotrimethylsilane, to provide a phthalocyanine compound, like phthalocyanine monomers, dimers or polymers, metalated or unmetalated, that are soluble in organic media.

Synthesis of Quaternary Carbon Stereogenic Centers through Enantioselective Cu-Catalyzed Allylic Substitutions with Vinylaluminum Reagents

PubMed Central

Gao, Fang; McGrath, Kevin P.; Lee, Yunmi; Hoveyda, Amir H.

2010-01-01

Catalytic enantioselective allylic substitution (EAS) reactions, which involve the use of alkyl- or aryl-substituted vinylaluminum reagents and afford 1,4-dienes containing a quaternary carbon stereogenic center at their C-3 site, are disclosed. The C–C bond forming transformations are promoted by 0.5–2.5 mol % of sulfonate bearing chiral bidentate N-heterocyclic carbene (NHC) complexes, furnishing the desired products efficiently (66–97% yield of isolated products) and in high site- (>98% SN2′) and enantioselectivity [up to 99:1 enantiomer ratio (er)]. To the best of our knowledge, the present report puts forward the first cases of allylic substitution reactions that result in the generation of all-carbon quaternary stereogenic centers through the addition of a vinyl unit. The aryl- and vinyl-substituted vinylaluminum reagents, which cannot be prepared in high efficiency through direct reaction with diisobutylaluminum hydride, are accessed through a recently introduced Ni-catalyzed reaction of the corresponding terminal alkynes with the same inexpensive metal-hydride agent. Sequential Ni-catalyzed hydrometallations and Cu-catalyzed C–C bond forming reactions allow for efficient and selective synthesis of a range of enantiomerically enriched EAS products, which cannot cannot be accessed by previously disclosed strategies (due to inefficient vinylmetal synthesis or low reactivity and/or selectivity with Si-substituted derivatives). The utility of the protocols developed is demonstrated through a concise enantioselective synthesis of natural product bakuchiol. PMID:20860365

Aptamer-recognized carbohydrates on the cell membrane revealed by super-resolution microscopy.

PubMed

Jing, Yingying; Cai, Mingjun; Xu, Haijiao; Zhou, Lulu; Yan, Qiuyan; Gao, Jing; Wang, Hongda

2018-04-26

Carbohydrates are one of the most important components on the cell membrane, which participate in various physiological activities, and their aberrant expression is a consequence of pathological changes. In previous studies, carbohydrate analysis basically relied on lectins. However, discrimination between lectins still exists due to their multivalent character. Furthermore, the structures obtained by carbohydrate-lectin crosslinking confuse our direct observation to some extent. Fortunately, the emergence of aptamers, which are smaller and more flexible, has provided us an unprecedented choice. Herein, an aptamer recognition method with high precise localization was developed for imaging membrane-bound N-acetylgalactosamine (GalNAc). By using direct stochastic optical reconstruction microscopy (dSTORM), we compared this aptamer recognition method with the lectin recognition method for visualizing the detailed structure of GalNAc at the nanometer scale. The results indicated that GalNAc forms irregular clusters on the cell membrane with a resolution of 23 ± 7 nm by aptamer recognition. Additionally, when treated with N-acetylgalactosidase, the aptamer-recognized GalNAc shows a more significant decrease in cluster size and localization density, thus verifying better specificity of aptamers than lectins. Collectively, our study suggests that aptamers can act as perfect substitutes for lectins in carbohydrate labeling, which will be of great potential value in the field of super-resolution fluorescence imaging.

Vacancy Mediated Mechanism of Nitrogen Substitution in Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Menon, Madhu; Sadanadan, Bindu; Rao, Apparao M.

2003-01-01

Nitrogen substitution reaction in a graphene sheet and carbon nanotubes of different diameter are investigated using the generalized tight-binding molecular dynamics method. The formation of a vacancy in curved graphene sheet or a carbon nanotube is found to cause a curvature dependent local reconstruction of the surface. Our simulations and analysis show that vacancy mediated N substitution (rather than N chemisorption) is favored on the surface of nanotubes with diameter larger than 8 nm. This predicted value of the critical minimum diameter for N incorporation is confirmed by experimental results presented.

The manufacture of synthetic non-sintered and degradable bone grafting substitutes.

PubMed

Gerike, W; Bienengräber, V; Henkel, K-O; Bayerlein, T; Proff, P; Gedrange, T; Gerber, Th

2006-02-01

A new synthetic bone grafting substitute (NanoBone, ARTOSS GmbH, Germany) is presented. This is produced by a new technique, the sol-gel-method. This bone grafting substitute consists of nanocrystalline hydroxyapatite (HA) and nanostructured silica (SiO2). By achieving a highly porous structure good osteoconductivity can be seen. In addition, the material will be completely biodegraded and new own bone is formed. It has been demonstrated that NanoBone is biodegraded by osteoclasts in a manner comparable to the natural bone remodelling process.

Comparison of advanced therapy medicinal product gingiva and skin substitutes and their in vitro wound healing potentials

PubMed Central

Boink, Mireille A.; Roffel, Sanne; Breetveld, Melanie; Thon, Maria; Haasjes, Michiel S.P.; Waaijman, Taco; Scheper, Rik J.; Blok, Chantal S.

2017-01-01

Abstract Skin and oral mucosa substitutes are a therapeutic option for closing hard‐to‐heal skin and oral wounds. Our aim was to develop bi‐layered skin and gingiva substitutes, from 3 mm diameter biopsies, cultured under identical conditions, which are compliant with current European regulations for advanced therapy medicinal products. We present in vitro mode of action methods to (i) determine viability: epithelial expansion, proliferation (Ki‐67), metabolic activity (MTT assay); (ii) characterize skin and gingiva substitutes: histology and immunohistochemistry; and (iii) determine potency: soluble wound healing mediator release (enzyme‐linked immunosorbent assay). Both skin and gingiva substitutes consist of metabolically active autologous reconstructed differentiated epithelium expanding from the original biopsy sheet on a fibroblast populated connective tissue matrix (donor dermis). Gingival epithelium expanded 1.7‐fold more than skin epithelium during the 3 week culture period. The percentage of proliferating Ki‐67‐positive cells located in the basal layer of the gingiva substitute was >1.5‐fold higher than in the skin substitute. Keratins 16 and 17, which are upregulated during normal wound healing, were expressed in both the skin and gingiva substitutes. Notably, the gingiva substitute secreted higher amounts of key cytokines involved in mitogenesis, motogenesis and chemotaxis (interleukin‐6 > 23‐fold, CXCL8 > 2.5‐fold) as well as higher amounts of the anti‐fibrotic growth factor, hepatocyte growth factor (>7‐fold), compared with the skin substitute. In conclusion, while addressing the viability, characterization and potency of the tissue substitutes, important intrinsic differences between skin and gingiva were discovered that may explain in part the superior quality of wound healing observed in the oral mucosa compared with skin. PMID:28388010

FRAGS: estimation of coding sequence substitution rates from fragmentary data

PubMed Central

Swart, Estienne C; Hide, Winston A; Seoighe, Cathal

2004-01-01

Background Rates of substitution in protein-coding sequences can provide important insights into evolutionary processes that are of biomedical and theoretical interest. Increased availability of coding sequence data has enabled researchers to estimate more accurately the coding sequence divergence of pairs of organisms. However the use of different data sources, alignment protocols and methods to estimate substitution rates leads to widely varying estimates of key parameters that define the coding sequence divergence of orthologous genes. Although complete genome sequence data are not available for all organisms, fragmentary sequence data can provide accurate estimates of substitution rates provided that an appropriate and consistent methodology is used and that differences in the estimates obtainable from different data sources are taken into account. Results We have developed FRAGS, an application framework that uses existing, freely available software components to construct in-frame alignments and estimate coding substitution rates from fragmentary sequence data. Coding sequence substitution estimates for human and chimpanzee sequences, generated by FRAGS, reveal that methodological differences can give rise to significantly different estimates of important substitution parameters. The estimated substitution rates were also used to infer upper-bounds on the amount of sequencing error in the datasets that we have analysed. Conclusion We have developed a system that performs robust estimation of substitution rates for orthologous sequences from a pair of organisms. Our system can be used when fragmentary genomic or transcript data is available from one of the organisms and the other is a completely sequenced genome within the Ensembl database. As well as estimating substitution statistics our system enables the user to manage and query alignment and substitution data. PMID:15005802

Enantioselective direct α-amination of aldehydes via a photoredox mechanism: a strategy for asymmetric amine fragment coupling.

PubMed

Cecere, Giuseppe; König, Christian M; Alleva, Jennifer L; MacMillan, David W C

2013-08-07

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated N-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Importantly, this photoinduced transformation allows direct and enantioselective access to α-amino aldehyde products that do not require postreaction manipulation.

Inulin determination for food labeling.

PubMed

Zuleta, A; Sambucetti, M E

2001-10-01

Inulin and oligofructose exhibit valuable nutritional and functional attributes, so they are used as supplements as soluble fiber or as macronutrient substitutes. As classic analytical methods for dietary fiber measurement are not effective, several specific methods have been proposed. These methods measure total fructans and are based on one or more enzymatic sample treatments and determination of released sugars. To determine inulin for labeling purposes, we developed an easy and rapid anion-exchange high-performance liquid chromatography (HPLC) method following water extraction of inulin. HPLC conditions included an Aminex HPX- 87C column (Bio-Rad), deionized water at 85 degrees C as the mobile phase and a refractive index detector. The tested foods included tailor-made food products containing known amounts of inulin and commercial products (cookies, milk, ice creams, cheese, and cereal bars). The average recovery was 97%, and the coefficient of variation ranged from 1.1 to 5% in the food matrixes. The obtained results showed that this method provides an easier, faster and cheaper alternative than previous techniques for determining inulin with enough accuracy and precision for routine labeling purposes by direct determination of inulin by HPLC with refractive index detection.

Methods of Technological Forecasting,

DTIC Science & Technology

1977-05-01

Trend Extrapolation Progress Curve Analogy Trend Correlation Substitution Analysis or Substitution Growth Curves Envelope Curve Advances in the State of...the Art Technological Mapping Contextual Mapping Matrix Input-Output Analysis Mathematical Models Simulation Models Dynamic Modelling. CHAPTER IV...Generation Interaction between Needs and Possibilities Map of the Technological Future — (‘ross- Impact Matri x Discovery Matrix Morphological Analysis

Sterically Hindered Square-Planar Nickel(II) Organometallic Complexes: Preparation, Characterization, and Substitution Behavior

ERIC Educational Resources Information Center

Martinez, Manuel; Muller, Guillermo; Rocamora, Merce; Rodriguez, Carlos

2007-01-01

The series of experiments proposed for advanced undergraduate students deal with both standard organometallic preparative methods in dry anaerobic conditions and with a kinetic study of the mechanisms operating in the substitution of square-planar complexes. The preparation of organometallic compounds is carried out by transmetallation or…

Feature-based classification of amino acid substitutions outside conserved functional protein domains.

PubMed

Gemovic, Branislava; Perovic, Vladimir; Glisic, Sanja; Veljkovic, Nevena

2013-01-01

There are more than 500 amino acid substitutions in each human genome, and bioinformatics tools irreplaceably contribute to determination of their functional effects. We have developed feature-based algorithm for the detection of mutations outside conserved functional domains (CFDs) and compared its classification efficacy with the most commonly used phylogeny-based tools, PolyPhen-2 and SIFT. The new algorithm is based on the informational spectrum method (ISM), a feature-based technique, and statistical analysis. Our dataset contained neutral polymorphisms and mutations associated with myeloid malignancies from epigenetic regulators ASXL1, DNMT3A, EZH2, and TET2. PolyPhen-2 and SIFT had significantly lower accuracies in predicting the effects of amino acid substitutions outside CFDs than expected, with especially low sensitivity. On the other hand, only ISM algorithm showed statistically significant classification of these sequences. It outperformed PolyPhen-2 and SIFT by 15% and 13%, respectively. These results suggest that feature-based methods, like ISM, are more suitable for the classification of amino acid substitutions outside CFDs than phylogeny-based tools.

Dialkylthio Substitution: An Effective Method to Modulate the Molecular Energy Levels of 2D-BDT Photovoltaic Polymers.

PubMed

Yao, Huifeng; Zhang, Hao; Ye, Long; Zhao, Wenchao; Zhang, Shaoqing; Hou, Jianhui

2016-02-17

Dialkylthio-substituted thienyl-benzodithiophene (BDT-DST) was designed and synthesized as a building block to modulate the molecular levels of the conjugated polymers, and three copolymers named PDST-BDD, PDST-TT and PDST-DPP were prepared and applied in polymer solar cells (PSCs). Theoretical calculations and electrochemical cyclic voltammetry (CV) measurement suggested that the dialkylthio group could decrease the molecular energy levels of the resulting polymers distinctly. The open-circuit voltage (VOC) of PSC devices based on PDST-BDD, PDST-TT, and PDST-DPP are as high as 1.0, 0.98, and 0.88 V, respectively, which are ∼0.15 V higher than those of the corresponding alky-substituted analogues. Moreover, the influence of the dialkylthio group on the absorption spectra, crystalline properties, hole mobilities, and blend morphologies of the polymers was also investigated. The results indicate that the dialkythio substitution is an effective method to modulate the molecular energy levels and that the BDT-DST unit has potential for constructing high-efficiency photovoltaic polymers.

The role of annealing temperature and bio template (egg white) on the structural, morphological and magnetic properties of manganese substituted MFe2O4 (M=Zn, Cu, Ni, Co) nanoparticles

NASA Astrophysics Data System (ADS)

Ranjith Kumar, E.; Jayaprakash, R.; Kumar, Sanjay

2014-02-01

Manganese substituted ferrites (ZnFe2O4, CuFe2O4, NiFe2O4 and CoFe2O4) have been prepared in the bio template medium by using a simple evaporation method. The annealing temperature plays an important position on changing particle size and morphology of the mixed ferrite nanoparticles were found out by X-ray diffraction, transmission electron microscopy and scanning electron microscopy methods. The role of manganese substitution in the mixed ferrite nanoparticles were also analyzed for different annealing temperature. The substitution of Mn also creates a vital change in magnetic properties which is studied by using vibrating sample magnetometer (VSM). These spinel ferrites are decomposed to α-Fe2O3 after annealing above 550 °C in air. However, α-Fe2O3 phase was slowly vanished after ferrites annealing above 900 °C. The effect of this secondary phase on the structural change and magnetic properties of the mixed ferrite nanoparticles is discussed.

48 CFR 852.236-72 - Performance of work by the contractor.

Code of Federal Regulations, 2012 CFR

2012-10-01

..., mechanics, and foremen/forewomen on the contractor's payroll and under his/her direct supervision shall be... System (NAS), substitute the following paragraphs (b) and (c) for paragraphs (b) and (c) of the basic...

48 CFR 852.236-72 - Performance of work by the contractor.

Code of Federal Regulations, 2014 CFR

2014-10-01

..., mechanics, and foremen/forewomen on the contractor's payroll and under his/her direct supervision shall be... System (NAS), substitute the following paragraphs (b) and (c) for paragraphs (b) and (c) of the basic...

48 CFR 852.236-72 - Performance of work by the contractor.

Code of Federal Regulations, 2011 CFR

2011-10-01

..., mechanics, and foremen/forewomen on the contractor's payroll and under his/her direct supervision shall be... System (NAS), substitute the following paragraphs (b) and (c) for paragraphs (b) and (c) of the basic...

48 CFR 852.236-72 - Performance of work by the contractor.

Code of Federal Regulations, 2013 CFR

2013-10-01

..., mechanics, and foremen/forewomen on the contractor's payroll and under his/her direct supervision shall be... System (NAS), substitute the following paragraphs (b) and (c) for paragraphs (b) and (c) of the basic...

Magnetocrystalline anisotropy of ɛ-Fe2O3

NASA Astrophysics Data System (ADS)

Ahamed, Imran; Pathak, Rohit; Skomski, Ralph; Kashyap, Arti

2018-05-01

The epsilon Fe2O3 phase of iron oxide has been studied to understand the spin structure and the magnetocrystalline anisotropy in the bulk and in thin films of ɛ-Fe2O3 and Co-doped ɛ-Fe2O3. The preferential magnetization direction in the nanoparticles of ɛ-Fe2O3 is along the a-axis [M. Gich et al., Chem. Mater. 18, 3889 (2006)]. Compared to the bulk band gap of 1.9 eV, the thin-film band gap is reduced to 1.3 eV in the Co-free films and to 0.7 eV in the film with partial Co substitution. The easy magnetization direction of the bulk and Co-free ɛ-Fe2O3 is along the c-axis, but it switches to the a-axis on Co substitution. All three systems exhibit in-plane anisotropies associated with the orthorhombic crystal structure of the oxide.

The RNA Polymerase II Trigger Loop Functions in Substrate Selection and is Directly Targeted by α-amanitin

PubMed Central

Kaplan, Craig D.; Larsson, Karl-Magnus; Kornberg, Roger D.

2008-01-01

Summary Structural, biochemical and genetic studies have led to proposals that a mobile element of multi-subunit RNA polymerases, the Trigger Loop (TL), plays a critical role in catalysis and can be targeted by antibiotic inhibitors. Here we present evidence that the Saccharomyces cerevisiae RNA Polymerase II (Pol II) TL participates in substrate selection. Amino acid substitutions within the Pol II TL preferentially alter substrate usage and enzyme fidelity, as does inhibition of transcription by α-amanitin. Finally, substitution of His1085 in the TL specifically renders Pol II highly resistant to α-amanitin, indicating a functional interaction between His1085 and α-amanitin that is supported by re-refinement of an α-amanitin-Pol II crystal structure. We propose that α-amanitin inhibited Pol II elongation, which is slow and exhibits reduced substrate selectivity, results from direct α-amanitin interference with the TL. PMID:18538653

Four chemical trends will shape the next decade's directions in Perfluoroalkyl and Polyfluoroalkyl substances research

NASA Astrophysics Data System (ADS)

Kotthoff, Matthias; Bücking, Mark

2018-04-01

Per- and polyfluoroalkyl substances (PFAS) represent a versatile group of ubiquitously occurring chemicals of increasing regulatory concern. The past years lead to an ever expanding portfolio of detected anthropogenic PFAS in numerous products encountered in daily life. Yet no clear picture of the full range of individual substance that comprise PFAS is available and this challenges analytical and engineering sciences. Authorities struggle to cope with uncertainties in managing risk of harm posed by PFAS.This is a result of an incomplete understanding of the range of compounds that they comprise in differing products. There are analytical uncertainties identifying PFAS and estimating the concentrations of the total PFAS loadindividual molecules remain unknown. There are four major trends from the chemical perspective that will shape PFAS research for the next decade. 1.Mobility: A wide and dynamic distribution of short chain PFAS due to their high polarity, persistency and volatility. 2.Substitution of regulated substances: The ban or restrictions of individual molecules will lead to a replacement with substitutes of similar concern. 3.Increase in structural diversity of existing PFAS molecules: Introduction of e.g. hydrogens and chlorine atoms instead of fluorine, as well as branching and cross-linking lead to a high versatility of unknown target molecules. 4. Unknown “Dark Matter”: The amount, identity, formation pathways, and transformation dynamics of polymers and PFAS precursors are largely unknown. These directions require optimized analytical setups, especially multi-methods, and semi-specific tools to determine PFAS-sum parameters in any relevant matrix.

Challenges to Implementing Opioid Substitution Therapy in Ukrainian Prisons: Personnel Attitudes Toward Addiction, Treatment, and People With HIV/AIDS

PubMed Central

Polonsky, Maxim; Azbel, Lyuba; Wickersham, Jeffrey A.; Taxman, Faye S.; Grishaev, Evgeny; Dvoryak, Sergey; Altice, Frederick L.

2015-01-01

Background Ukraine is experiencing one of the most volatile HIV epidemics globally, fueled primarily by people who inject drugs (PWIDs), and a parallel incarceration epidemic. Opioid substitution therapy (OST) is internationally recognized as one of the most effective forms of treatment for opioid dependence and is among the most effective HIV prevention strategies available, yet efforts to adopt it in Ukraine’s Criminal Justice System (CJS) have been thwarted. Methods To understand the reluctance of the Ukrainian CJS to adopt OST despite the overwhelming evidence pointing to its health benefits and improved criminal justice outcomes, we conducted the first survey of Ukrainian prison administrative, medical and custodial staff (N=243) attitudes towards addiction in general, OST, and people living with HIV/AIDS (PLWHA) in representative regions of Ukraine. Results Results revealed that Ukrainian CJS workers’ attitudes toward OST, PLWHA, and drug addiction were universally negative, but differed substantially along geographic and occupational lines. Whereas geographic and cultural proximity to the European Union drove positive attitudes in the west, in the southern region we observed an identifiability effect, as workers who worked directly with prisoners held the most positive attitudes. We also found that knowledge mediated the effect of drug intolerance on OST attitudes. Conclusion In Ukraine, adoption of OST is more influenced by ideological biases and prejudices than by existing scientific evidence. By elucidating existing attitudes among CJS personnel, this assessment will help direct subsequent interventions to address the barriers to implementing evidence-based HIV prevention treatments. PMID:25620732

Time Series Analysis on the Impact of Generic Substitution and Reference Pricing on Antipsychotic Costs in Finland.

PubMed

Koskinen, Hanna; Mikkola, Hennamari; Saastamoinen, Leena K; Ahola, Elina; Martikainen, Jaana E

2015-12-01

To analyze the medium- to long-term impact of generic substitution and the reference price system on the daily cost of antipsychotics in Finland. The additional impact of reference pricing over and above previously implemented generic substitution was also assessed. An interrupted time series design with a control group and segmented regression analysis was used to estimate the effect of the implementation of generic substitution and the reference price system on the daily cost of antipsychotics. The data have 69 monthly values of the average daily cost for each of the studied antipsychotics: 39 months before and 30 months after the introduction of reference pricing. For one of the studied antipsychotic, the time before the introduction of reference pricing could be further divided into time before and after the introduction of generic substitution. According to the model, 2.5 years after the implementation of reference pricing, the daily cost of the studied antipsychotics was 24.6% to 50.6% lower than it would have been if reference pricing had not been implemented. Two and a half years after the implementation of the reference price system, however, the additional impact of reference pricing over and above previously implemented generic substitution was modest, less than 1 percentage point. Although the price competition induced by reference pricing decreased the prices of antipsychotics in Finland in the short-term, the prices had a tendency to stagnate or even to turn in an upward direction in the medium- to long-term. Furthermore, the additional impact of reference pricing over and above previously implemented generic substitution remained quite modest. Copyright © 2015 International Society for Pharmacoeconomics and Outcomes Research (ISPOR). Published by Elsevier Inc. All rights reserved.

Fish mislabelling in France: substitution rates and retail types.

PubMed

Bénard-Capelle, Julien; Guillonneau, Victoire; Nouvian, Claire; Fournier, Nicolas; Le Loët, Karine; Dettai, Agnès

2015-01-01

Market policies have profound implications for consumers as well as for the management of resources. One of the major concerns in fish trading is species mislabelling: the commercial name used does not correspond to the product, most often because the product is in fact a cheaper or a more easily available species. Substitution rates depend heavily on species, some often being sold mislabelled while others rarely or never mislabelled. Rates also vary largely depending on countries. In this study, we analyse the first market-wide dataset collected for France, the largest sea food market in Europe, for fish species substitution. We sequenced and analysed 371 samples bearing 55 commercial species names, collected in fishmonger shops, supermarkets and restaurants; the largest dataset assembled to date in an European country. Sampling included fish fillets, both fresh and frozen, and prepared meals. We found a total of 14 cases of mislabelling in five species: bluefin tuna, cod, yellowfin tuna, sole and seabream, setting the overall substitution rate at 3.7% CI [2.2-6.4], one of the lowest observed for comparable surveys with large sampling. We detected no case of species mislabelling among the frozen fillets or in industrially prepared meals, and all the substitutions were observed in products sold in fishmongers shops or restaurants. The rate of mislabelling does not differ between species, except for bluefin tuna. Despite a very small sample size ( n = 6), the rate observed for this species (83.3% CI [36-99]) stands in sharp contrast with the low substitution rate observed for the other substituted species. In agreement with studies from other countries, this work shows that fish mislabelling can vary greatly within a country depending on the species. It further suggests that more efforts should be directed to the control of high value species like bluefin tuna.

Substantial Regional Variation in Substitution Rates in the Human Genome: Importance of GC Content, Gene Density, and Telomere-Specific Effects

NASA Astrophysics Data System (ADS)

Arndt, Peter F.; Hwa, Terence; Petrov, Dmitri A.

2005-06-01

This study presents the first global, 1 Mbp level analysis of patterns of nucleotide substitutions along the human lineage. The study is based on the analysis of a large amount of repetitive elements deposited into the human genome since the mammalian radiation, yielding a number of results that would have been difficult to obtain using the more conventional comparative method of analysis. This analysis revealed substantial and consistent variability of rates of substitution, with the variability ranging up to 2-fold among different regions. The rates of substitutions of C or G nucleotides with A or T nucleotides vary much more sharply than the reverse rates suggesting that much of that variation is due to differences in mutation rates rather than in the probabilities of fixation of C/G vs. A/T nucleotides across the genome. For all types of substitution we observe substantially more hotspots than coldspots, with hotspots showing substantial clustering over tens of Mbp's. Our analysis revealed that GC-content of surrounding sequences is the best predictor of the rates of substitution. The pattern of substitution appears very different near telomeres compared to the rest of the genome and cannot be explained by the genome-wide correlations of the substitution rates with GC content or exon density. The telomere pattern of substitution is consistent with natural selection or biased gene conversion acting to increase the GC-content of the sequences that are within 10-15 Mbp away from the telomere.

Environmentally safe aviation fuels

NASA Technical Reports Server (NTRS)

Liberio, Patricia D.

1995-01-01

In response to the Air Force directive to remove Ozone Depleting Chemicals (ODC's) from military specifications and Defense Logistics Agency's Hazardous Waste Minimization Program, we are faced with how to ensure a quality aviation fuel without using such chemicals. Many of these chemicals are found throughout the fuel and fuel related military specifications and are part of test methods that help qualify the properties and quality of the fuels before they are procured. Many years ago there was a directive for military specifications to use commercially standard test methods in order to provide standard testing in private industry and government. As a result the test methods used in military specifications are governed by the American Society of Testing and Materials (ASTM). The Air Force has been very proactive in the removal or replacement of the ODC's and hazardous materials in these test methods. For example, ASTM D3703 (Standard Test Method for Peroxide Number of Aviation Turbine Fuels), requires the use of Freon 113, a known ODC. A new rapid, portable hydroperoxide test for jet fuels similar to ASTM D3703 that does not require the use of ODC's has been developed. This test has proved, in limited testing, to be a viable substitute method for ASTM D3703. The Air Force is currently conducting a round robin to allow the method to be accepted by ASTM and therefore replace the current method. This paper will describe the Air Force's initiatives to remove ODC's and hazardous materials from the fuel and fuel related military specifications that the Air Force Wright Laboratory.

Electric Power Distribution System Model Simplification Using Segment Substitution

DOE PAGES

Reiman, Andrew P.; McDermott, Thomas E.; Akcakaya, Murat; ...

2017-09-20

Quasi-static time-series (QSTS) simulation is used to simulate the behavior of distribution systems over long periods of time (typically hours to years). The technique involves repeatedly solving the load-flow problem for a distribution system model and is useful for distributed energy resource (DER) planning. When a QSTS simulation has a small time step and a long duration, the computational burden of the simulation can be a barrier to integration into utility workflows. One way to relieve the computational burden is to simplify the system model. The segment substitution method of simplifying distribution system models introduced in this paper offers modelmore » bus reduction of up to 98% with a simplification error as low as 0.2% (0.002 pu voltage). Finally, in contrast to existing methods of distribution system model simplification, which rely on topological inspection and linearization, the segment substitution method uses black-box segment data and an assumed simplified topology.« less

Magnetic properties of co-precipitated hexaferrite powders with Sm-Co substitutions optimized with the molten flux method

NASA Astrophysics Data System (ADS)

Serletis, C.; Litsardakis, G.; Pavlidou, E.; Efthimiadis, K. G.

2017-11-01

In this work, using the chemical coprecipitation method, Sr1-xSmxFe12-xCoxO19 (x = 0, 0.1, 0.2) hexaferrite powders were prepared. Major magnetization loops were recorded at room temperature in order to determine the correct calcination temperature for optimum hard magnetic properties. It is found that a small degree of substitution increases substantially the coercive field. Also, the use of the molten flux calcination method increases the remanent magnetization. SEM/EDXS and XRD measurements were performed at the calcined powders: the results show that a single hexaferrite phase is formed and that the substituted powders consist of an assembly of grains with a mean diameter of 40 nm. Measurements of minor magnetization loops and of the temperature and time dependence of the magnetization confirm that the powders consist of a non-oriented single domain magnetic particles assembly. The results indicate that Sm could be a viable replacement for La in the manufacturing of hexaferrites with a high-energy product.

Electric Power Distribution System Model Simplification Using Segment Substitution

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

Reiman, Andrew P.; McDermott, Thomas E.; Akcakaya, Murat

Quasi-static time-series (QSTS) simulation is used to simulate the behavior of distribution systems over long periods of time (typically hours to years). The technique involves repeatedly solving the load-flow problem for a distribution system model and is useful for distributed energy resource (DER) planning. When a QSTS simulation has a small time step and a long duration, the computational burden of the simulation can be a barrier to integration into utility workflows. One way to relieve the computational burden is to simplify the system model. The segment substitution method of simplifying distribution system models introduced in this paper offers modelmore » bus reduction of up to 98% with a simplification error as low as 0.2% (0.002 pu voltage). Finally, in contrast to existing methods of distribution system model simplification, which rely on topological inspection and linearization, the segment substitution method uses black-box segment data and an assumed simplified topology.« less

An odor interaction model of binary odorant mixtures by a partial differential equation method.

PubMed

Yan, Luchun; Liu, Jiemin; Wang, Guihua; Wu, Chuandong

2014-07-09

A novel odor interaction model was proposed for binary mixtures of benzene and substituted benzenes by a partial differential equation (PDE) method. Based on the measurement method (tangent-intercept method) of partial molar volume, original parameters of corresponding formulas were reasonably displaced by perceptual measures. By these substitutions, it was possible to relate a mixture's odor intensity to the individual odorant's relative odor activity value (OAV). Several binary mixtures of benzene and substituted benzenes were respectively tested to establish the PDE models. The obtained results showed that the PDE model provided an easily interpretable method relating individual components to their joint odor intensity. Besides, both predictive performance and feasibility of the PDE model were proved well through a series of odor intensity matching tests. If combining the PDE model with portable gas detectors or on-line monitoring systems, olfactory evaluation of odor intensity will be achieved by instruments instead of odor assessors. Many disadvantages (e.g., expense on a fixed number of odor assessors) also will be successfully avoided. Thus, the PDE model is predicted to be helpful to the monitoring and management of odor pollutions.

Enduring powers of attorney: promoting attorneys' accountability as substitute decision makers.

PubMed

Tilse, Cheryl; Wilson, Jill; White, Ben; Willmott, Lindy; McCawley, Anne-Louise

2014-09-01

The misuse and abuse of Enduring Powers of Attorney (EPAs) by attorneys, particularly in relation to financial decision-making, is a growing concern. This paper explores the opportunities to enhance accountability of attorneys at the time of the execution of the document in Queensland. A four-stage multi-method design comprised a critical reference group; semi-structured interviews with 32 principals or potential principals, attorneys and witnesses; two focus groups with service providers and a state-wide survey of 76 principals, attorneys and witnesses. Across all methods and user groups, understanding the role and obligations of the attorney in an EPA was consistently identified as problematic. Promoting accountability and understanding can be addressed by greater attention to the role of the attorney in the forms/ guidelines and in the structure and witnessing of the forms, increased direction about record keeping and access to appropriate advice and support. © 2013 ACOTA.

Pd-Catalyzed regioselective intramolecular dehydrogenative C-5 cross coupling in an N-substituted pyrrole-azole system.

PubMed

Tripathi, Krishna N; Ray, Devalina; Singh, Ravi P

2017-12-06

Functionalized polycyclic pyrrole-azole structures possessing fused six membered and seven membered rings were directly synthesized via ligand-enabled, Pd-catalyzed, site selective, intramolecular cross couplings of N-substituted pyrrole-azoles. C5-H activation in the presence of a reactive C2-H remains a challenge that needs to be addressed and this was targeted to be resolved through the present approach by specifically generating the cyclized products with 83-100% selectivity. The featured methodology provides a novel disconnection for the synthesis of pyrrole containing alkaloids and medicinal compounds.

Mutational Dynamics of Aroid Chloroplast Genomes

PubMed Central

Ahmed, Ibrar; Biggs, Patrick J.; Matthews, Peter J.; Collins, Lesley J.; Hendy, Michael D.; Lockhart, Peter J.

2012-01-01

A characteristic feature of eukaryote and prokaryote genomes is the co-occurrence of nucleotide substitution and insertion/deletion (indel) mutations. Although similar observations have also been made for chloroplast DNA, genome-wide associations have not been reported. We determined the chloroplast genome sequences for two morphotypes of taro (Colocasia esculenta; family Araceae) and compared these with four publicly available aroid chloroplast genomes. Here, we report the extent of genome-wide association between direct and inverted repeats, indels, and substitutions in these aroid chloroplast genomes. We suggest that alternative but not mutually exclusive hypotheses explain the mutational dynamics of chloroplast genome evolution. PMID:23204304

Manpower Substitution and Productivity in Medical Practice

PubMed Central

Reinhardt, Uwe E.

1973-01-01

Probably in response to the often alleged physician shortage in this country, concerted research efforts are under way to identify technically feasible opportunities for manpower substitution in the production of ambulatory health care. The approaches range from descriptive studies of the effect of task delegation on output of medical services to rigorous mathematical modeling of health care production by means of linear or continuous production functions. In this article the distinct methodological approaches underlying mathematical models are presented in synopsis, and their inherent strengths and weaknesses are contrasted. The discussion includes suggestions for future research directions. Images Fig. 2 PMID:4586735

Charged defects in two-dimensional semiconductors of arbitrary thickness and geometry: Formulation and application to few-layer black phosphorus

NASA Astrophysics Data System (ADS)

Wang, Dan; Han, Dong; Li, Xian-Bin; Chen, Nian-Ke; West, Damien; Meunier, Vincent; Zhang, Shengbai; Sun, Hong-Bo

2017-10-01

Energy evaluation of charged defects is tremendously important in two-dimensional (2D) semiconductors for the industrialization of 2D electronic devices because of its close relation with the corresponding type of conductivity and its strength. Although the method to calculate the energy of charged defects in single-layer one-atom-thick systems of equilateral unit-cell geometry has recently been proposed, few-layer 2D semiconductors are more common in device applications. As it turns out, one may not apply the one-layer formalism to multilayer cases without jeopardizing accuracy. Here, we generalize the approach to 2D systems of arbitrary cell geometry and thickness and use few-layer black phosphorus to illustrate how defect properties, mainly group-VI substitutional impurities, are affected. Within the framework of density functional theory, we show that substitutional Te (T eP) is the best candidate for n -type doping, and as the thickness increases, the ionization energy is found to decrease monotonically from 0.67 eV (monolayer) to 0.47 eV (bilayer) and further to 0.33 eV (trilayer). Although these results show the ineffectiveness of the dielectric screening at the monolayer limit, they also show how it evolves with increasing thickness whereby setting a new direction for the design of 2D electronics. The proposed method here is generally suitable to all the 2D materials regardless of their thickness and geometry.

Dielectric and AC conductivity studies of Nd substituted 0.8BaTiO{sub 3}-0.2(Bi{sub 0.5(1-x)}Nd{sub 0.5x}K{sub 0.5})TiO{sub 3} lead free ceramics

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

Ramesh, M. N. V.; Ramesh, K. V., E-mail: kv-ramesh5@yahoo.co.in

2016-05-23

0.8BaTiO{sub 3} – 0.2(Bi{sub 0.5(1-x)}Nd{sub 0.5x}K{sub 0.5})TiO{sub 3} (0.01 ≤ x ≤ 0.06) lead free ceramic materials have been prepared by solid state reaction method and followed by high energy ball milling process. X-ray diffraction studies confirm the tetragonal structure of the materials at room temperature. Lattice parameters and density are decreasing with increase of Nd substitution. Microstructure studies were done by using Scanning electron microscope and it found that grain size is decreasing with increase of Nd substitution. Temperature and frequency dependent dielectric studies reveal relaxor behaviour of the materials. Dielectric constant, dielectric loss and Curie temperature are decreasingmore » with Nd substitution. Maximum Curie temperature of 195°C was observed at 1 MHz for x=0.01 Nd substituted sample. Degree of diffuseness was calculated from the modified Curie-Weiss law and it is increasing with Nd substitution. AC conductivity is increasing with increase of Nd substitution and observed maximum activation energy of 0.52 eV for x=0.02 Nd substituted sample.« less

Phosphorus doped graphene by inductively coupled plasma and triphenylphosphine treatments

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

Shin, Dong-Wook, E-mail: shindong37@skku.edu; Kim, Tae Sung; Yoo, Ji-Beom, E-mail: jbyoo@skku.edu

Highlights: • Substitution doping is a promising method for opening the energy band gap of graphene. • Substitution doping with phosphorus in the graphene lattice has numerous advantage such as high band gap, low formation energy, and high net charge density compared to nitrogen. • V{sub dirac} of Inductively coupled plasma (ICP) and triphenylphosphine (TPP) treated graphene was −57 V, which provided clear evidence of n-type doping. • Substitutional doping of graphene with phosphorus is verified by the XPS spectra of P 2p core level and EELS mapping of phosphorus. • The chemical bonding between P and graphene is verymore » stable for a long time in air (2 months). - Abstract: Graphene is considered a host material for various applications in next-generation electronic devices. However, despite its excellent properties, one of the most important issues to be solved as an electronic material is the creation of an energy band gap. Substitution doping is a promising method for opening the energy band gap of graphene. Herein, we demonstrate the substitutional doping of graphene with phosphorus using inductively coupled plasma (ICP) and triphenylphosphine (TPP) treatments. The electrical transfer characteristics of the phosphorus doped graphene field effect transistor (GFET) have a V{sub dirac} of ∼ − 54 V. The chemical bonding between P and C was clearly observed in XPS spectra, and uniform distribution of phosphorus within graphene domains was confirmed by EELS mapping. The capability for substitutional doping of graphene with phosphorus can significantly promote the development of graphene based electronic devices.« less

First-principles study on alkali-metal effect of Li, Na, and K in CuInSe2 and CuGaSe2

NASA Astrophysics Data System (ADS)

Maeda, Tsuyoshi; Kawabata, Atsuhito; Wada, Takahiro

2015-08-01

The substitution energies and migration energies of the alkali metal atoms of Li, Na, and K in CuInSe2 (CIS) and CuGaSe2 (CGS) were investigated by first-principles calculations. The substitution energies of Li, Na, and K atoms in CIS and CGS were calculated for two different cationic atom positions of Cu and In/Ga in the chalcopyrite unit cell. In CIS and CGS, the substitution energies of NaCu are much lower than those of NaIn and NaGa. The substitution energies of the LiCu atoms in CIS and CGS are lower than those of NaCu, while the substitution energies of KCu atoms in CIS and CGS are much higher than those of NaCu. Therefore, it is difficult to form KCu in CIS and CGS. The migration energies of Li, Na, and K atoms in CIS and CGS are obtained by a combination of the linear and quadratic synchronous transit (LST/QST) methods and the nudged elastic band (NEB) method. The theoretical migration energies of a Na atom at the Cu site to the nearest Cu vacancy (NaCu → VCu) in CIS and CGS are much lower than those of (CuCu → VCu) in CIS and CGS. The mechanism underlying the alkali metal effect of Li, Na, and K in the CIGS film during the post-deposition treatment of LiF, NaF, and KF is discussed on the basis of the calculated substitution and migration energies.

Directed evolution of P-glycoprotein cysteines reveals site-specific, non-conservative substitutions that preserve multidrug resistance.

PubMed

Swartz, Douglas J; Mok, Leo; Botta, Sri K; Singh, Anukriti; Altenberg, Guillermo A; Urbatsch, Ina L

2014-06-25

Pgp (P-glycoprotein) is a prototype ABC (ATP-binding-cassette) transporter involved in multidrug resistance of cancer. We used directed evolution to replace six cytoplasmic Cys (cysteine) residues in Pgp with all 20 standard amino acids and selected for active mutants. From a pool of 75000 transformants for each block of three Cys, we identified multiple mutants that preserved drug resistance and yeast mating activity. The most frequent substitutions were glycine and serine for Cys427 (24 and 20%, respectively) and Cys1070 (37 and 25%) of the Walker A motifs in the NBDs (nucleotide-binding domains), Cys1223 in NBD2 (25 and 8%) and Cys638 in the linker region (24 and 16%), whereas close-by Cys669 tolerated glycine (16%) and alanine (14%), but not serine (absent). Cys1121 in NBD2 showed a clear preference for positively charged arginine (38%) suggesting a salt bridge with Glu269 in the ICL2 (intracellular loop 2) may stabilize domain interactions. In contrast, three Cys residues in transmembrane α-helices could be successfully replaced by alanine. The resulting CL (Cys-less) Pgp was fully active in yeast cells, and purified proteins displayed drug-stimulated ATPase activities indistinguishable from WT (wild-type) Pgp. Overall, directed evolution identified site-specific, non-conservative Cys substitutions that allowed building of a robust CL Pgp, an invaluable new tool for future functional and structural studies, and that may guide the construction of other CL proteins where alanine and serine have proven unsuccessful.

Effects of Al substitution and thermal annealing on magnetoelectric Ba0.5Sr1.5Zn2Fe12O22 investigated by the enhancement factor of 57Fe nuclear magnetic resonance.

PubMed

Kwon, Sangil; Kang, Byeongki; Kim, Changsoo; Jo, Euna; Lee, Soonchil; Chai, Yi Sheng; Chun, Sae Hwan; Kim, Kee Hoon

2014-04-09

The magnetoelectric properties of hexaferrite Ba0.5Sr1.5Zn2Fe12O22 are significantly improved by Al substitution and thermal annealing. Measuring the enhancement factor of 57Fe NMR, we found direct microscopic evidence that the magnetic moments of the L and S blocks are rotated by a magnetic field in such a way as to increase the net magnetic moment of a magnetic unit, even after the field is removed. Al substitution makes magnetoelectric property arise easily by suppressing the easy-plane anisotropy. The effect of thermal annealing is to stabilize the multiferroic state by reducing the number of pinning sites and the electron spin fluctuation. The transverse conic structure gradually changes to the alternating longitudinal conic structure where spins fluctuate more severely.

Substitution of saturated fat in processed meat products: a review.

PubMed

Ospina-E, J C; Sierra-C, A; Ochoa, O; Pérez-Álvarez, J A; Fernández-López, J

2012-01-01

The food industry is increasingly directing its efforts to produce and commercialize functional foods where the reduction or even elimination of saturated fat is an important goal. This situation arises from the concern of many institutions and individuals worldwide on the growth of non-transmissible diseases, particularly cardiovascular ones. This article presents a revision of the most important research carried out on processed meat products production and looks at the topic from two principal points of view: the nutritional and technological function of fat and the way in which it is gradually being replaced in the above-mentioned products. Many ingredients have been used to substitute fat but while the results concerning the nutritional composition of the final products are generally acceptable, the sensory aspects are not completely solved. This review emphasizes the use of plastic fats because they allow the highest fat substitution levels during its process and consumption without affecting the product behavior.

Nucleotide exchange and excision technology DNA shuffling and directed evolution.

PubMed

Speck, Janina; Stebel, Sabine C; Arndt, Katja M; Müller, Kristian M

2011-01-01

Remarkable success in optimizing complex properties within DNA and proteins has been achieved by directed evolution. In contrast to various random mutagenesis methods and high-throughput selection methods, the number of available DNA shuffling procedures is limited, and protocols are often difficult to adjust. The strength of the nucleotide exchange and excision technology (NExT) DNA shuffling described here is the robust, efficient, and easily controllable DNA fragmentation step based on random incorporation of the so-called 'exchange nucleotides' by PCR. The exchange nucleotides are removed enzymatically, followed by chemical cleavage of the DNA backbone. The oligonucleotide pool is reassembled into full-length genes by internal primer extension, and the recombined gene library is amplified by standard PCR. The technique has been demonstrated by shuffling a defined gene library of chloramphenicol acetyltransferase variants using uridine as fragmentation defining exchange nucleotide. Substituting 33% of the dTTP with dUTP in the incorporation PCR resulted in shuffled clones with an average parental fragment size of 86 bases and revealed a mutation rate of only 0.1%. Additionally, a computer program (NExTProg) has been developed that predicts the fragment size distribution depending on the relative amount of the exchange nucleotide.

Structure-Function Analysis of Chloroplast Proteins via Random Mutagenesis Using Error-Prone PCR.

PubMed

Dumas, Louis; Zito, Francesca; Auroy, Pascaline; Johnson, Xenie; Peltier, Gilles; Alric, Jean

2018-06-01

Site-directed mutagenesis of chloroplast genes was developed three decades ago and has greatly advanced the field of photosynthesis research. Here, we describe a new approach for generating random chloroplast gene mutants that combines error-prone polymerase chain reaction of a gene of interest with chloroplast complementation of the knockout Chlamydomonas reinhardtii mutant. As a proof of concept, we targeted a 300-bp sequence of the petD gene that encodes subunit IV of the thylakoid membrane-bound cytochrome b 6 f complex. By sequencing chloroplast transformants, we revealed 149 mutations in the 300-bp target petD sequence that resulted in 92 amino acid substitutions in the 100-residue target subunit IV sequence. Our results show that this method is suited to the study of highly hydrophobic, multisubunit, and chloroplast-encoded proteins containing cofactors such as hemes, iron-sulfur clusters, and chlorophyll pigments. Moreover, we show that mutant screening and sequencing can be used to study photosynthetic mechanisms or to probe the mutational robustness of chloroplast-encoded proteins, and we propose that this method is a valuable tool for the directed evolution of enzymes in the chloroplast. © 2018 American Society of Plant Biologists. All rights reserved.

Limited memory Broyden-Fletcher-Goldfarb-Shanno (L-BFGS) method for the parameter estimation on geographically weighted ordinal logistic regression model (GWOLR)

NASA Astrophysics Data System (ADS)

Saputro, Dewi Retno Sari; Widyaningsih, Purnami

2017-08-01

In general, the parameter estimation of GWOLR model uses maximum likelihood method, but it constructs a system of nonlinear equations, making it difficult to find the solution. Therefore, an approximate solution is needed. There are two popular numerical methods: the methods of Newton and Quasi-Newton (QN). Newton's method requires large-scale time in executing the computation program since it contains Jacobian matrix (derivative). QN method overcomes the drawback of Newton's method by substituting derivative computation into a function of direct computation. The QN method uses Hessian matrix approach which contains Davidon-Fletcher-Powell (DFP) formula. The Broyden-Fletcher-Goldfarb-Shanno (BFGS) method is categorized as the QN method which has the DFP formula attribute of having positive definite Hessian matrix. The BFGS method requires large memory in executing the program so another algorithm to decrease memory usage is needed, namely Low Memory BFGS (LBFGS). The purpose of this research is to compute the efficiency of the LBFGS method in the iterative and recursive computation of Hessian matrix and its inverse for the GWOLR parameter estimation. In reference to the research findings, we found out that the BFGS and LBFGS methods have arithmetic operation schemes, including O(n2) and O(nm).

A rapid and reliable PCR method for genotyping the ABO blood group. II: A2 and O2 alleles.

PubMed

O'Keefe, D S; Dobrovic, A

1996-01-01

PCR permits direct genotyping of individuals at the ABO locus. Several methods have been reported for genotyping ABO that rely on differentiating the A, B, and O alleles at specific base substitutions. However, the O allele as defined by serology comprises at least two alleles (O1 and O2) at the molecular level, and most current ABO genotyping methods only take into account the O1 allele. Determining the presence of the O2 allele is critical, as this not-infrequent allele would be mistyped as an A or a B allele by standard PCR typing methods. Furthermore, none of the methods to date distinguish between the A1 and A2 alleles, even though 10% of all white persons are blood group A2. We have developed a method for genotyping the ABO locus that takes the O2 and A2 alleles into account. Typing for A2 and O2 by diagnostic restriction enzyme digestion is a sensitive, nonradioactive assay that provides a convenient method useful for forensic and paternity testing and for clarifying anomalous serological results.

Preparation of polycrystalline FeTe1- x S x ( x = 0.00-0.30) via solid-state reaction method at ambient pressure

NASA Astrophysics Data System (ADS)

Lim, Edmund H. H.; Liew, Josephine Y. C.; Awang Kechik, M. M.; Halim, S. A.; Chen, S. K.; Tan, K. B.; Qi, X.

2017-06-01

Polycrystalline samples with nominal composition FeTe1- x S x ( x = 0.00-0.30) were synthesized via solid state reaction method with intermittent grinding in argon gas flow. X-ray diffraction (XRD) patterns revealed the tetragonal structure (space group P4/nmm) of the samples with the presence of impurities Fe3O4 and FeTe2. By substitution with S, the a and c lattice parameters shrink probably due to the smaller ionic radius of S2- compared to Te2-. Scanning electron microscopy images showed that the samples developed plate-like grains with increasing S substitution. Substitution of Te with S suppresses the structural transition of the parent compound FeTe as shown by both the temperature dependence of resistance and magnetic moment measurements. All of the S-substituted samples showed a rapid drop of resistance at around 9-10 K but zero resistance down to 4 K was not observed. In addition, negative magnetic moment corresponds to diamagnetism was detected in the samples for x = 0.25 and 0.30 suggesting the coexistence of magnetic and superconducting phase in these samples. The magnetization hysteresis loops measured at room temperature showed ferromagnetic behavior for the pure and S substituted samples. However, the magnetization, rentivity and coercivity decreased with S content.

Ab-initio Study of the Electron Mobility in a Functionalized UiO-66 Metal Organic Framework

NASA Astrophysics Data System (ADS)

Musho, Terence D.; Yasin, Alhassan S.

2018-03-01

This study leverages density functional theory accompanied with Boltzmann transport equation approaches to investigate the electronic mobility as a function of inorganic substitution and functionalization in a thermally stable UiO-66 metal-organic framework (MOF). The MOFs investigated are based on Zr-UiO-66 MOF with three functionalization groups of benzene dicarboxylate (BDC), BDC functionalized with an amino group (BDC + NH_2 ) and a nitro group (BDC + NO_2 ). The design space of this study is bound by UiO-66(M)-R, [M=Zr , Ti, Hf; R=BDC , BDC+NO_2 , BDC+NH_2 ]. The elastic modulus was not found to vary significantly over the structural modification of the design space for either functionalization or inorganic substitution. However, the electron-phonon scattering potential was found to be controllable by up to 30% through controlled inorganic substitution in the metal clusters of the MOF structure. The highest electron mobility was predicted for a UiO-66(Hf_5Zr_1 ) achieving a value of approximately 1.4× 10^{-3} cm^2 /V s. It was determined that functionalization provides a controlled method of modulating the charge density, while inorganic substitution provides a controlled method of modulating the electronic mobility. Within the proposed design space the electrical conductivity was able to be increased by approximately three times the base conductivity through a combination of inorganic substitution and functionalization.

Ab-initio Study of the Electron Mobility in a Functionalized UiO-66 Metal Organic Framework

NASA Astrophysics Data System (ADS)

Musho, Terence D.; Yasin, Alhassan S.

2018-07-01

This study leverages density functional theory accompanied with Boltzmann transport equation approaches to investigate the electronic mobility as a function of inorganic substitution and functionalization in a thermally stable UiO-66 metal-organic framework (MOF). The MOFs investigated are based on Zr-UiO-66 MOF with three functionalization groups of benzene dicarboxylate (BDC), BDC functionalized with an amino group (BDC + NH_2) and a nitro group (BDC + NO_2). The design space of this study is bound by UiO-66(M)-R, [M=Zr, Ti, Hf; R=BDC, BDC+NO_2, BDC+NH_2]. The elastic modulus was not found to vary significantly over the structural modification of the design space for either functionalization or inorganic substitution. However, the electron-phonon scattering potential was found to be controllable by up to 30% through controlled inorganic substitution in the metal clusters of the MOF structure. The highest electron mobility was predicted for a UiO-66(Hf_5Zr_1) achieving a value of approximately 1.4× 10^{-3} cm^2/V s. It was determined that functionalization provides a controlled method of modulating the charge density, while inorganic substitution provides a controlled method of modulating the electronic mobility. Within the proposed design space the electrical conductivity was able to be increased by approximately three times the base conductivity through a combination of inorganic substitution and functionalization.

Stepping stones for biological invasion: A bioeconomic model of transferable risk

Treesearch

Travis Warziniack; David Finnoff; Jonathan Bossenbroek; Jason F. Shogren; David Lodge

2011-01-01

We investigate three sources of bias in valuation methods for ecosystem risk: failure to consider substitution possibilities between goods, failure to consider nonseparability of ecosystem services with market goods, and failure to consider substitution possibilities between ecosystems. The first two biases are known in the literature, and we offer insight on the size...

Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Processes.

PubMed

Fu, Gregory C

2017-07-26

Classical methods for achieving nucleophilic substitutions of alkyl electrophiles (S N 1 and S N 2) have limited scope and are not generally amenable to enantioselective variants that employ readily available racemic electrophiles. Radical-based pathways catalyzed by chiral transition-metal complexes provide an attractive approach to addressing these limitations.

Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Processes

PubMed Central

2017-01-01

Classical methods for achieving nucleophilic substitutions of alkyl electrophiles (SN1 and SN2) have limited scope and are not generally amenable to enantioselective variants that employ readily available racemic electrophiles. Radical-based pathways catalyzed by chiral transition-metal complexes provide an attractive approach to addressing these limitations. PMID:28776010

Copper-Catalyzed Heteroarylboration of 1,3-Dienes with 3-Bromopyridines: A cine Substitution.

PubMed

Smith, Kevin B; Huang, Yuan; Brown, M Kevin

2018-04-26

A method for the heteroarylboration of 1,3-dienes is presented. The process involves an unusual cine substitution of 3-bromopyridine derivatives to deliver highly functionalized heterocyclic products. Mechanistic studies are included that clarify the details of this unusual process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles.

PubMed

Bala, Manju; Verma, Praveen Kumar; Sharma, Deepika; Kumar, Neeraj; Singh, Bikram

2015-05-01

An efficient water-catalyzed method has been developed for the synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles in one step. The present method excludes the usage of toxic metal catalysts and bases to produce benzazoles in good to excellent yields. An efficient and versatile water-mediated method has been established for the synthesis of various 2-arylbenzazoles. The present protocol excludes the usage of any catalyst and additive provided excellent selectivities and yields with high functional group tolerance for the synthesis of 2-arylated benzimidazoles, benzoxazoles, and benzothiazoles. Benzazolones were also synthesized using similar reaction protocol.

Comparison of the Discriminative Stimulus Effects of Dimethyltryptamine with Different Classes of Psychoactive Compounds in Rats

PubMed Central

Gatch, Michael B.; Rutledge, Margaret A.; Carbonaro, Theresa; Forster, Michael J.

2010-01-01

Rationale There has been increased recreational use of dimethyltryptamine (DMT), but little is known of its discriminative stimulus effects. Objectives The present study assessed the similarity of the discriminative stimulus effects of DMT to other types of hallucinogens and to psychostimulants. Methods Rats were trained to discriminate DMT from saline. To test the similarity of DMT to known hallucinogens, the ability of (+)-lysergic acid diethylamide (LSD), (−)-2,5-dimethoxy-4-methylamphetamine (DOM), (+)-methamphetamine, or (±)3,4-methylenedioxymethyl-amphetamine (MDMA) to substitute in DMT-trained rats was tested. The ability of DMT to substitute in rats trained to discriminate each of these compounds was also tested. To assess the degree of similarity in discriminative stimulus effects, each of the compounds was tested for substitution in all of the other training groups. Results LSD, DOM, and MDMA all fully substituted in DMT-trained rats, whereas DMT fully substituted only in DOM-trained rats. Full cross-substitution occurred between DMT and DOM, LSD and DOM, and (+)-methamphetamine and MDMA. MDMA fully substituted for (+)-methamphetamine, DOM, and DMT, but only partially for LSD. In MDMA-trained rats, LSD and (+)-methamphetamine fully substituted, whereas DMT and DOM did not fully substitute. No cross-substitution was evident between (+)-methamphetamine and DMT, LSD, or DOM. Conclusions DMT produces discriminative stimulus effects most similar to those of DOM, with some similarity to the discriminative stimulus effects of LSD and MDMA. Like DOM and LSD, DMT seems to produce predominately hallucinogenic-like discriminative stimulus effects and minimal psychostimulant effects, in contrast to MDMA which produced hallucinogen- and psychostimulant-like effects. PMID:19288085

Intake of low sodium salt substitute for 3years attenuates the increase in blood pressure in a rural population of North China - A randomized controlled trial.

PubMed

Zhou, Bo; Webster, Jacqui; Fu, Ling-Yu; Wang, Hai-Long; Wu, Xiao-Mei; Wang, Wen-Li; Shi, Jing-Pu

2016-07-15

Lowering salt intake is one of the successful and cost-effective methods to reduce blood pressure (BP). In this randomized controlled study, we investigated the effects of a 3-year substitution of table salt with a low-sodium salt substitute in a rural population of North China. Subjects from 200 families residing in five villages in Liaoning, North China were registered in this study and randomly divided into two groups: normal salt (100% sodium chloride) and low salt substitute (65% NaCl, 25% KCl, 10% MgSO4). We compared the effects of the low-sodium salt substitute and normal salt on differences in BP from baseline to various follow-up time points during this 3-year study period. We also examined several factors that may affect the long-term changes in BP. Hypertension was defined per World Health Organization guidelines as BP≥140/90mmHg. The low sodium substitute significantly reduced the increase in both systolic and diastolic BP compared with the regular salt (P=0.000). Also, the population aged 40-70years showed most beneficial response to the salt substitute compared with those aged <40 or >70years. The low salt substitute had similar beneficial effects in both males and females. In addition, the salt type consumed and body mass index significantly affected the change in BP. Use of the salt substitute significantly reduces the increase in BP over a long term, and thus, the salt substitute can be used as a replacement for regular salt in the daily diet to prevent/diminish the incidence of hypertension. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Protein substitute dosage in PKU: how much do young patients need?

PubMed Central

MacDonald, A; Chakrapani, A; Hendriksz, C; Daly, A; Davies, P; Asplin, D; Hall, K; Booth, I W

2006-01-01

Background The optimal dose of protein substitute has not been determined in children with phenylketonuria (PKU). Aim To determine if a lower dose of protein substitute could achieve the same or better degree of blood phenylalanine control when compared to the dosage recommended by the UK MRC.1 Methods In a six week randomised, crossover study, two doses of protein substitute (Protocol A: 2 g/kg/day of protein equivalent; Protocol B: 1.2 g/kg/day protein equivalent) were compared in 25 children with well controlled PKU aged 2–10 years (median 6 years). Each dose of protein substitute was taken for 14 days, with a 14 day washout period in between. Twice daily blood samples (fasting pre‐breakfast and evening, at standard times) for plasma phenylalanine were taken on day 8–14 of each protocol. The median usual dose of protein substitute was 2.2 g/kg/day (range 1.5–3.1 g/kg/day). Results When compared with control values, median plasma phenylalanine on the low dose of protein substitute increased at pre‐breakfast by 301 μmol/l (95% CI 215 to 386) and in the evening by 337 μmol/l (95% CI 248 to 431). On the high dose of protein substitute, plasma phenylalanine concentrations remained unchanged when compared to control values. However, wide variability was seen between subjects. Conclusions A higher dosage of protein substitute appeared to contribute to lower blood phenylalanine concentrations in PKU, but it did have a variable and individual impact and may have been influenced by the carbohydrate (+/− fat) content of the protein substitute. PMID:16547085

Using mid-level cadres as substitutes for internationally mobile health professionals in Africa. A desk review

PubMed Central

Dovlo, Delanyo

2004-01-01

Background Substitute health workers are cadres who take on some of the functions and roles normally reserved for internationally recognized health professionals such as doctors, pharmacists and nurses but who usually receive shorter pre-service training and possess lower qualifications. Methods A desk review is conducted on the education, regulation, scopes of practice, specialization, nomenclature, retention and cost-effectiveness of substitute health workers in terms of their utilization in countries such as Tanzania, Malawi, Mozambique, Zambia, Ghana etc., using curricula, evaluations and key-informant questionnaires. Results The cost-effectiveness of using substitutes and their relative retention within countries and in rural communities underlies their advantages to African health systems. Some studies comparing clinical officers and doctors show minimal differences in outcomes to patients. Specialized substitutes provide services in disciplines such as surgery, ophthalmology, orthopedics, radiology, dermatology, anesthesiology and dentistry, demonstrating a general bias of use for clinical services. Conclusions The findings raise interest in expanding the use of substitute cadres, as the demands of expanding access to services such as antiretroviral treatment requires substantial human resources capacity. Understanding the roles and conditions under which such cadres best function, and managing the skepticism and professional turf protection that restricts their potential, will assist in effective utilization of substitutes. PMID:15207010

Exploration of hydrophobic modification degree of chitosan-based nanocomplexes on the oral delivery of enoxaparin.

PubMed

Wang, Linlin; Li, Liang; Sun, Yujiao; Tian, Ye; Li, Ying; Li, Conghao; Junyaprasert, Varaporn B; Mao, Shirui

2013-11-20

The objective of this paper is to elucidate the influence of lipophilic modification degree of chitosan on the peroral absorption of enoxaparin. A series of novel chitosan grafted glyceryl monostearate (GM) copolymers with different GM substitution degree were synthesized and the successful synthesis was confirmed by (1)H NMR, FTIR and X-ray diffraction. Enoxaparin loaded nanocomplexes with different carriers were prepared by self-assembly process. Influence of GM substitution degree and chitosan molecular weight in the copolymer on the properties of the nanocomplexes was investigated. Morphology of the nanocomplexes was observed by atomic force microscopy. Mucoadhesive properties of the nanocomplexes were characterized using mucin particle method. Initially, mucoadhesion of the nanocomplexes increased with the increase of GM substitution degree and it started to decrease when the substitution degree was up to 18.6%. A good linear relationship between GM substitution degree and in vivo absorption of enoxaparin in fasted rats was established in the substitution degree range of 0-11.1%. In agreement with mucoadhesion data, further increasing GM substitution degree to 18.6% caused a decrease in oral absorption. In conclusion, oral bioavailability of enoxaparin can be enhanced by structure modification of the carriers and the bioavailability is hydrophobic modification degree dependent. Copyright © 2013 Elsevier B.V. All rights reserved.

Tissue engineering for urinary tract reconstruction and repair: Progress and prospect in China.

PubMed

Zou, Qingsong; Fu, Qiang

2018-04-01

Several urinary tract pathologic conditions, such as strictures, cancer, and obliterations, require reconstructive plastic surgery. Reconstruction of the urinary tract is an intractable task for urologists due to insufficient autologous tissue. Limitations of autologous tissue application prompted urologists to investigate ideal substitutes. Tissue engineering is a new direction in these cases. Advances in tissue engineering over the last 2 decades may offer alternative approaches for the urinary tract reconstruction. The main components of tissue engineering include biomaterials and cells. Biomaterials can be used with or without cultured cells. This paper focuses on cell sources, biomaterials, and existing methods of tissue engineering for urinary tract reconstruction in China. The paper also details challenges and perspectives involved in urinary tract reconstruction.

Recognition and Sensing of Creatinine.

PubMed

Guinovart, Tomàs; Hernández-Alonso, Daniel; Adriaenssens, Louis; Blondeau, Pascal; Martínez-Belmonte, Marta; Rius, F Xavier; Andrade, Francisco J; Ballester, Pablo

2016-02-12

Current methods for creatinine quantification suffer from significant drawbacks when aiming to combine accuracy, simplicity, and affordability. Here, an unprecedented synthetic receptor, an aryl-substituted calix[4]pyrrole with a monophosphonate bridge, is reported that displays remarkable affinity for creatinine and the creatininium cation. The receptor works by including the guest in its deep and polar aromatic cavity and establishing directional interactions in three dimensions. When incorporated into a suitable polymeric membrane, this molecule acts as an ionophore. A highly sensitive and selective potentiometric sensor suitable for the determination of creatinine levels in biological fluids, such as urine or plasma, in an accurate, fast, simple, and cost-effective way has thus been developed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic acid from CO2.

PubMed

Yadav, Rajesh K; Baeg, Jin-Ook; Oh, Gyu Hwan; Park, No-Joong; Kong, Ki-jeong; Kim, Jinheung; Hwang, Dong Won; Biswas, Soumya K

2012-07-18

The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO(2). The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO(2).

Crl binds to domain 2 of σ(S) and confers a competitive advantage on a natural rpoS mutant of Salmonella enterica serovar Typhi.

PubMed

Monteil, Véronique; Kolb, Annie; Mayer, Claudine; Hoos, Sylviane; England, Patrick; Norel, Françoise

2010-12-01

The RpoS sigma factor (σ(S)) is the master regulator of the bacterial response to a variety of stresses. Mutants in rpoS arise in bacterial populations in the absence of stress, probably as a consequence of a subtle balance between self-preservation and nutritional competence. We characterized here one natural rpoS mutant of Salmonella enterica serovar Typhi (Ty19). We show that the rpoS allele of Ty19 (rpoS(Ty19)) led to the synthesis of a σ(S)(Ty19) protein carrying a single glycine-to-valine substitution at position 282 in σ(S) domain 4, which was much more dependent than the wild-type σ(S) protein on activation by Crl, a chaperone-like protein that increases the affinity of σ(S) for the RNA polymerase core enzyme (E). We used the bacterial adenylate cyclase two-hybrid system to demonstrate that Crl bound to residues 72 to 167 of σ(S) domain 2 and that G282V substitution did not directly affect Crl binding. However, this substitution drastically reduced the ability of σ(S)(Ty19) to bind E in a surface plasmon resonance assay, a defect partially rescued by Crl. The modeled structure of the Eσ(S) holoenzyme suggested that substitution G282V could directly disrupt a favorable interaction between σ(S) and E. The rpoS(Ty19) allele conferred a competitive fitness when the bacterial population was wild type for crl but was outcompeted in Δcrl populations. Thus, these results indicate that the competitive advantage of the rpoS(Ty19) mutant is dependent on Crl and suggest that crl plays a role in the appearance of rpoS mutants in bacterial populations.

Direct detection by real-time PCR of ftsI gene mutations affecting MICs of β-lactam agents for Haemophilus influenzae isolates from meningitis.

PubMed

Kishii, Kozue; Morozumi, Miyuki; Chiba, Naoko; Ono, Akiko; Ubukata, Kimiko

2011-10-01

One resistance mechanism of Haemophilus influenzae to ampicillin involves decreased affinity of penicillin-binding protein (PBP) 3 for β-lactam antibiotics reflecting amino acid substitutions in PBP3 encoded by the ftsI gene. Three amino acid substitutions, Ser385Thr, Arg517His, and Asn526Lys, are especially responsible for β-lactam resistance. We constructed a new real-time polymerase chain reaction (PCR) to directly detect these substitutions in addition to 16S ribosomal RNA (rRNA), cap, and bla(TEM) genes. Our real-time PCR was evaluated using 206 clinical H. influenzae strains isolated from pediatric patients with meningitis. Relative sensitivities and specificities of real-time PCR were 90.5-100% and 96.3-100% for all resistance classes compared with our previously reported conventional PCR. In addition, real-time PCR shortened time required from 3 h by conventional PCR to 1.5 h. When correlations between combinations of amino acid substitutions in the ftsI gene detected by real-time PCR and minimum inhibitory concentrations (MICs) of β-lactam antibiotics were evaluated, MIC(90)s of ampicillin for β-lactamase-nonproducing ampicillin-intermediate-resistant strains with Asn526Lys, β-lactamase-nonproducing, ampicillin-resistant strains with Ser385Thr, and β-lactamase-nonproducing ampicillin-resistant strains with both Asn526Lys and Ser385Thr, respectively, were two, four, and eight times higher than those for sensitive strains. Similarly, MIC(90)s of cephalosporins for these strains, respectively, were two, 16-32, and 16-32 times higher than those for sensitive strains. Thus, real-time PCR can guide antibiotic use.

Bacterial Two-Hybrid Analysis of Interactions between Region 4 of the ς70 Subunit of RNA Polymerase and the Transcriptional Regulators Rsd from Escherichia coli and AlgQ from Pseudomonas aeruginosa

PubMed Central

Dove, Simon L.; Hochschild, Ann

2001-01-01

A number of transcriptional regulators mediate their effects through direct contact with the ς70 subunit of Escherichia coli RNA polymerase (RNAP). In particular, several regulators have been shown to contact a C-terminal portion of ς70 that harbors conserved region 4. This region of ς contains a putative helix-turn-helix DNA-binding motif that contacts the −35 element of ς70-dependent promoters directly. Here we report the use of a recently developed bacterial two-hybrid system to study the interaction between the putative anti-ς factor Rsd and the ς70 subunit of E. coli RNAP. Using this system, we found that Rsd can interact with an 86-amino-acid C-terminal fragment of ς70 and also that amino acid substitution R596H, within region 4 of ς70, weakens this interaction. We demonstrated the specificity of this effect by showing that substitution R596H does not weaken the interaction between ς and two other regulators shown previously to contact region 4 of ς70. We also demonstrated that AlgQ, a homolog of Rsd that positively regulates virulence gene expression in Pseudomonas aeruginosa, can contact the C-terminal region of the ς70 subunit of RNAP from this organism. We found that amino acid substitution R600H in ς70 from P. aeruginosa, corresponding to the R596H substitution in E. coli ς70, specifically weakens the interaction between AlgQ and ς70. Taken together, our findings suggest that Rsd and AlgQ contact similar surfaces of RNAP present in region 4 of ς70 and probably regulate gene expression through this contact. PMID:11591686

Evolution of flavone synthase I from parsley flavanone 3beta-hydroxylase by site-directed mutagenesis.

PubMed

Gebhardt, Yvonne Helen; Witte, Simone; Steuber, Holger; Matern, Ulrich; Martens, Stefan

2007-07-01

Flavanone 3beta-hydroxylase (FHT) and flavone synthase I (FNS I) are 2-oxoglutarate-dependent dioxygenases with 80% sequence identity, which catalyze distinct reactions in flavonoid biosynthesis. However, FNS I has been reported exclusively from a few Apiaceae species, whereas FHTs are more abundant. Domain-swapping experiments joining the N terminus of parsley (Petroselinum crispum) FHT with the C terminus of parsley FNS I and vice versa revealed that the C-terminal portion is not essential for FNS I activity. Sequence alignments identified 26 amino acid substitutions conserved in FHT versus FNS I genes. Homology modeling, based on the related anthocyanidin synthase structure, assigned seven of these amino acids (FHT/FNS I, M106T, I115T, V116I, I131F, D195E, V200I, L215V, and K216R) to the active site. Accordingly, FHT was modified by site-directed mutagenesis, creating mutants encoding from one to seven substitutions, which were expressed in yeast (Saccharomyces cerevisiae) for FNS I and FHT assays. The exchange I131F in combination with either M106T and D195E or L215V and K216R replacements was sufficient to confer some FNS I side activity. Introduction of all seven FNS I substitutions into the FHT sequence, however, caused a nearly complete change in enzyme activity from FHT to FNS I. Both FHT and FNS I were proposed to initially withdraw the beta-face-configured hydrogen from carbon-3 of the naringenin substrate. Our results suggest that the 7-fold substitution affects the orientation of the substrate in the active-site pocket such that this is followed by syn-elimination of hydrogen from carbon-2 (FNS I reaction) rather than the rebound hydroxylation of carbon-3 (FHT reaction).