Novel High Efficient Organic Photovoltaic Materials: Appendix for Summary of Research. Appendix

NASA Technical Reports Server (NTRS)

Sun, Sam

2002-01-01

There are many different kinds of conjugated polymers that may be useful in photovoltaic devices. So far, the most popular and successful conjugated polymers used in photovoltaic devices include poly(1,4-)phenylenevinylenes (PPV), C60 and their derivatives. The discovery of electro-luminescence in PPV has stimulated a great deal of interest in developing "plastic" solid-state semiconductor devices. The overall synthetic methodology for the preparation of PPV can be divided into three main categories: (1) side chain derivatization, (2) precursor approach, and (3) in-situ polymerization. In this project, the first method was adopted. As discussed in project proposal and literatures, the overall efficiency of photovoltaic devices containing conjugated polymers is determined by the materials ability to generate excitons from incoming radiation, and then to separate the charges at donor/acceptor interfaces, and then to transport charges to respective electrodes. Given that effective exciton diffusion range are typical less then 30 nm, unique morphological structures are needed. This need led to several research groups to the idea that interpenetrating or bi-continuous networks of donor (electron donating) and acceptor (electron withdrawing) polymers should give better results. One approach involved the use of functionalized PPV. The attachment of electron withdrawing cyano groups to a PPV forms the CN-PPV, making it a strong electron acceptor. Underivatized PPV is a generally considered a hole-transporting material. Using blends of MEH-PPV, a soluble donor PPV derivative, as a hole transporter and CN-PPV as an electron transporter, a quantum efficiencies of up to 6% was achieved.

5 CFR 1650.41 - How to obtain an age-based withdrawal.

Code of Federal Regulations, 2010 CFR

2010-01-01

... record keeper a properly completed paper TSP age-based withdrawal request form or use the TSP Web site to initiate a request. A participant's ability to complete an age-based withdrawal on the Web will depend on his or her retirement system coverage, marital status, and whether or not part or all of the...

Polymerization catalysts containing electron-withdrawing amide ligands

DOEpatents

Watkin, John G.; Click, Damon R.

2002-01-01

The present invention describes methods of making a series of amine-containing organic compounds which are used as ligands for group 3-10 and lanthanide metal compounds. The ligands have electron-withdrawing groups bonded to them. The metal compounds, when combined with a cocatalyst, are catalysts for the polymerization of olefins.

Comparison of the effects of the uncompetitive N-methyl-D-aspartate antagonist (+-)-5-aminocarbonyl-10,11-dihydro-5H-dibenzo[a,d] cyclohepten-5,10-imine (ADCI) with its structural analogs dizocilpine (MK-801) and carbamazepine on ethanol withdrawal seizures.

PubMed

Grant, K A; Snell, L D; Rogawski, M A; Thurkauf, A; Tabakoff, B

1992-03-01

The ability of [(+-)-5-aminocarbonyl-10,11-dihydro-5H-di-benzo [a,d]cyclohepten-5,10-imine (ADCI) and its structural analogs dizocilipine (MK-801) and carbamazepine to block ethanol withdrawal seizures was tested in mice made physically dependent upon ethanol. Three injections of either ADCI (ranging from 1.0-10.0 mg/kg), dizocilpine (ranging from 0.1-1.0 mg/kg) or carbamazepine (ranging from 17-50 mg/kg) were administered during the first 7 hr of ethanol withdrawal. The severity of ethanol withdrawal seizures was rated during the first 11 hr of withdrawal and again at 24 hr after withdrawal of ethanol. ADCI and dizocilpine suppressed the severity and occurrence of the withdrawal seizures in a dose-dependent fashion, whereas carbamazepine was ineffective in blocking the withdrawal seizures. The relative potencies of dizocilpine, ADCI and carbamazepine in suppressing ethanol withdrawal seizures corresponded with the relative potencies of the compounds in displacing [3H]dizocilpine from mouse cortical membrane preparations. These findings are consistent with the suggestion that blockade of N-methyl-D-aspartate-mediated neurotransmission is an effective treatment for decreasing ethanol withdrawal seizures. ADCI also blocked the occurrence of withdrawal-associated whole body tremors, whereas dizocilpine and carbamazepine were ineffective in blocking the tremors. The doses of ADCI, dizocilpine and carbamazepine that resulted in motor incoordination on an accelerating rotarod task were determined in groups of naive mice. Dizocilpine in doses as low as 0.3 mg/kg produced a decreased ability to remain on the rotarod, whereas ADCI up to 30 mg/kg did not affect rotarod performance.(ABSTRACT TRUNCATED AT 250 WORDS)

Successful withdrawal from high-dose benzodiazepine in a young patient through electronic monitoring of polypharmacy: a case report in an ambulatory setting.

PubMed

Loscertales, Hèctor R; Wentzky, Valerie; Dürsteler, Kenneth; Strasser, Johannes; Hersberger, Kurt E; Arnet, Isabelle

2017-05-01

Dependence on high-dose benzodiazepines (BZDs) is well known and discontinuation attempts are generally unsuccessful. A well established protocol for high-dose BZD withdrawal management is lacking. We present the case of withdrawal from high-dose lorazepam (>20 mg daily) in an unemployed 35-year-old male outpatient through agonist substitution with long-acting clonazepam and electronic monitoring over 28 weeks. All medicines were repacked into weekly 7 × 4 cavity multidose punch cards with an electronic monitoring system. The prescribed daily dosages of BZDs were translated into an optimal number of daily tablets, divided into up to four units of use. Withdrawal was achieved by individual leftover of a small quantity of BZDs that was placed in a separate compartment. Feedback with visualization of intake over the past week was given during weekly psychosocial sessions. Stepwise reduction was obtained by reducing the mg content of the cavities proportionally to the leftovers, keeping the number of cavities in order to maintain regular intake behavior, and to determine the dosage decrease. At week 28, the primary objectives were achieved, that is, lorazepam reduction to 5 mg daily and cannabis abstinence. Therapy was continued using multidrug punch cards without electronic monitoring to maintain the management system. At week 48, a smaller size weekly pill organizer with detachable daily containers was dispensed. At week 68, the patient's therapy was constant with 1.5 mg clonazepam + 5 mg lorazepam daily for anxiety symptoms and the last steps of withdrawal were started. Several key factors led to successful withdrawal from high-dose BZD in this outpatient, such as the use of weekly punch cards coupled with electronic monitoring, the patient's empowerment over the withdrawal process, and the collaboration of several healthcare professionals. The major implication for clinical care is reduction by following the leftovers, and not a diktat from the healthcare professionals.

5 CFR 1650.42 - How to obtain a financial hardship withdrawal.

Code of Federal Regulations, 2010 CFR

2010-01-01

... form or use the TSP Web site to initiate a request. A participant's ability to complete a financial hardship withdrawal on the Web will depend on his or her retirement system coverage and marital status. (b...

Controlling the Conformational Energy of a Phenyl Group by Tuning the Strength of a Nonclassical CH···O Hydrogen Bond: The Case of 5-Phenyl-1,3-dioxane.

PubMed

Bailey, William F; Lambert, Kyle M; Stempel, Zachary D; Wiberg, Kenneth B; Mercado, Brandon Q

2016-12-16

Anancomeric 5-phenyl-1,3-dioxanes provide a unique opportunity to study factors that control conformation. Whereas one might expect an axial phenyl group at C(5) of 1,3-dioxane to adopt a conformation similar to that in axial phenylcyclohexane, a series of studies including X-ray crystallography, NOE measurements, and DFT calculations demonstrate that the phenyl prefers to lie over the dioxane ring in order to position an ortho-hydrogen to participate in a stabilizing, nonclassical CH···O hydrogen bond with a ring oxygen of the dioxane. Acid-catalyzed equilibration of a series of anancomeric 2-tert-butyl-5-aryl-1,3-dioxane isomers demonstrates that remote substituents on the phenyl ring affect the conformational energy of a 5-aryl-1,3-dioxane: electron-withdrawing substituents decrease the conformational energy of the aryl group, while electron-donating substituents increase the conformational energy of the group. This effect is correlated in a very linear way to Hammett substituent parameters. In short, the strength of the CH···O hydrogen bond may be tuned in a predictable way in response to the electron-withdrawing or electron-donating ability of substituents positioned remotely on the aryl ring. This effect may be profound: a 3,5-bis-CF 3 phenyl group at C(5) in 1,3-dioxane displays a pronounced preference for the axial orientation. The results are relevant to broader conformational issues involving heterocyclic systems bearing aryl substituents.

Can Electron-Rich Oxygen (O2-) Withdraw Electrons from Metal Centers? A DFT Study on Oxoanion-Caged Polyoxometalates.

PubMed

Takazaki, Aki; Eda, Kazuo; Osakai, Toshiyuki; Nakajima, Takahito

2017-10-12

The answer to the question "Can electron-rich oxygen (O 2- ) withdraw electrons from metal centers?" is seemingly simple, but how the electron population on the M atom behaves when the O-M distance changes is a matter of controversy. A case study has been conducted for Keggin-type polyoxometalate (POM) complexes, and the first-principles electronic structure calculations were carried out not only for real POM species but also for "hypothetical" ones whose heteroatom was replaced with a point charge. From the results of natural population analysis, it was proven that even an electron-rich O 2- , owing to its larger electronegativity as a neutral atom, withdraws electrons when electron redistribution occurs by the change of the bond length. In the case where O 2- coexists with a cation having a large positive charge (e.g., P 5+ (O 2- ) 4 = [PO 4 ] 3- ), the gross electron population (GEP) on the M atom seemingly increases as the O atom comes closer, but this increment in GEP is not due to the role of the O atom but due to a Coulombic effect of the positive charge located on the cation. Furthermore, it was suggested that not GEP but net electron population (NEP) should be responsible for the redox properties.

Theoretical study of X⁻ · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH₂ and AsH₂): noncovalently electron-withdrawing effects on anion-arene interactions.

PubMed

Chen, Yishan; Yao, Lifeng

2014-01-01

The ternary complexes X(-) · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2) have been investigated by MP2 calculations to understand the noncovalently electron-withdrawing effects on anion-arene interactions. The results indicate that in binary complexes (1 · X(-)), both weak σ-type and anion-π complexes can be formed for Cl(-) and Br(-), but only anion-π complex can be formed for I(-). Moreover, the hydrogen-bonding complex is the global minimum for all three halides in binary complexes. However, in ternary complexes, anion-π complex become unstable and only σ complex can retain in many cases for Cl(-) and Br(-). Anion-π complex keeps stable only when YF = HF. In contrast with binary complexes, σ complex become the global minimum for Cl(-) and Br(-) in ternary complexes. These changes in binding mode and strength are consistent with the results of covalently electron-withdrawing effects. However, in contrast with the covalently electron-withdrawing substituents, Cl(-) and Br(-) can attack the aromatic carbon atom to form a strong σ complex when the noncovalently electron-withdrawing effect is induced by halogen bonding. The binding behavior for I(-) is different from that for Cl(-) and Br(-) in two aspects. First, the anion-π complex for I(-) can also keep stable when the noncovalent interaction is halogen bonding. Second, the anion-π complex for I(-) is the global minimum when it can retain as a stable structure.

Changes in Withdrawal and Craving Scores in Participants Undergoing Opioid Detoxification Utilizing Ibogaine.

PubMed

Malcolm, Benjamin J; Polanco, Martin; Barsuglia, Joseph P

2018-04-02

Opioid use disorder (OUD) is currently an epidemic in the United States (US) and ibogaine is reported to have the ability to interrupt opioid addiction by simultaneously mitigating withdrawal and craving symptoms. This study examined opioid withdrawal and drug craving scores in 50 participants with OUD undergoing a week-long detoxification treatment protocol with ibogaine. The Addiction Severity Index (ASI) was used for baseline characterization of participants' OUD. Clinical Opioid Withdrawal Scale (COWS), Subjective Opioid Withdrawal Scale (SOWS), and Brief Substance Craving Scale (BSCS) scores were collected at 48 and 24 hours prior to ibogaine administration, as well as 24 and 48 hours after ibogaine administration. At 48 hours following ibogaine administration, withdrawal and craving scores were significantly lowered in comparison to baseline: 78% of patients did not exhibit objective clinical signs of opioid withdrawal, 79% reported minimal cravings for opioids, and 68% reported subjective withdrawal symptoms in the mild range. Ibogaine appears to facilitate opioid detoxification by reducing opioid withdrawal and craving in participants with OUD. These results warrant further research using rigorous controlled trials.

Social withdrawal of persons with vascular dementia associated with disturbance of basic daily activities, apathy, and impaired social judgment.

PubMed

Honda, Yukiko; Meguro, Kenichi; Meguro, Mitsue; Akanuma, Kyoko

2013-01-01

Patients with vascular dementia (VaD) are often isolated, withdrawn from society because of negative symptoms and functional disabilities. The aim of this study was to detect factors associated with social withdrawal in patients with VaD. The participants were 36 institutionalized patients with VaD. Social withdrawal was assessed with the social withdrawal of the Multidimensional Observation Scale for Elderly Subjects (MOSES). Possible explanatory variables were the MOSES items depression and self-care, Cognitive Abilities Screening Instrument (CASI), apathy evaluation scale (AES), and Behavioral Pathology in Alzheimer's Disease Frequency-Weighted Severity Scale (BEHAVE-AD-FW). Multiple regression analyses were conducted for two groups: Analysis 1 was performed in all patients (N = 36) and Analysis 2 was performed in the patients with the ability to move by themselves (i.e., independent walking or independent movement with a cane or a wheelchair; n = 28). In Analysis 1, MOSES item social withdrawal was correlated with AES and MOSES item self-care. In Analysis 2, MOSES item social withdrawal was correlated with AES and CASI domain abstraction and judgment. Decreased social activities of VaD were not related to general cognitive function or depression. Disturbed activities of daily living (ADLs) for self-care may involve decreased frontal lobe function, indicating that comprehensive rehabilitation for both ADL and dementia are needed to improve the social activities of patients with VaD.

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

PubMed

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

2014-06-28

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

48 CFR 14.303 - Modification or withdrawal of bids.

Code of Federal Regulations, 2013 CFR

2013-10-01

... for the bid. (c) Upon withdrawal of an electronically transmitted bid, the data received shall not be viewed and shall be purged from primary and backup data storage systems. [48 FR 42171, Sept. 19, 1983, as...

48 CFR 14.303 - Modification or withdrawal of bids.

Code of Federal Regulations, 2012 CFR

2012-10-01

... for the bid. (c) Upon withdrawal of an electronically transmitted bid, the data received shall not be viewed and shall be purged from primary and backup data storage systems. [48 FR 42171, Sept. 19, 1983, as...

48 CFR 14.303 - Modification or withdrawal of bids.

Code of Federal Regulations, 2010 CFR

2010-10-01

... for the bid. (c) Upon withdrawal of an electronically transmitted bid, the data received shall not be viewed and shall be purged from primary and backup data storage systems. [48 FR 42171, Sept. 19, 1983, as...

48 CFR 14.303 - Modification or withdrawal of bids.

Code of Federal Regulations, 2014 CFR

2014-10-01

... for the bid. (c) Upon withdrawal of an electronically transmitted bid, the data received shall not be viewed and shall be purged from primary and backup data storage systems. [48 FR 42171, Sept. 19, 1983, as...

48 CFR 14.303 - Modification or withdrawal of bids.

Code of Federal Regulations, 2011 CFR

2011-10-01

... for the bid. (c) Upon withdrawal of an electronically transmitted bid, the data received shall not be viewed and shall be purged from primary and backup data storage systems. [48 FR 42171, Sept. 19, 1983, as...

DFT studies on the ligand effect on electronic and optical properties of three series of functionalized Ir(III) complexes

NASA Astrophysics Data System (ADS)

Liu, Shujie; Li, Yangen; Hu, Xiaoying; Liu, Xiangdong; Guan, Bo

2018-01-01

With the help of DFT and TDDFT, a series of functionalized mononuclear iridium (III) complexes were systematically investigated to make clear the effect of auxiliary ligands on their electrionic and photophysical properties. It can be found that introducing electron withdrawing group (sbnd CF3) on benzene moiety can stabilize HOMO level, thus leading to wider HOMO-LUMO gap and blue shift in spectrum. More importantly, introducing sbnd CF3 on benzene moiety can also significantly improve the radiative decay rate (kr). On the other hand, the incorporation of electron donating groups (such as -Ph(CH3)3) into pyridine moiety on ligand reduce kr. The complexes 1c-3c and 1d-3d have improved charge balance ability and larger percentage of metal character. The results revealed the nature of the different substituents have a significant effect on the HOMO, LUMO energy levels and kr, resulting in the change of emission color and the quantum efficiency (Φp).

Predictors of nicotine withdrawal symptoms: findings from the first randomized smoking cessation trial in a low-income country setting.

PubMed

Ben Taleb, Ziyad; Ward, Kenneth D; Asfar, Taghrid; Jaber, Rana; Auf, Rehab; Maziak, Wasim

2016-07-01

To identify predictors of nicotine withdrawal symptoms among smokers who participated in a randomized cessation trial in a low-income country. We analyzed data from 269 smokers who participated in a randomized, placebo-controlled smoking cessation trial conducted in primary healthcare in Aleppo, Syria. All participants received behavioral counseling and were randomized to receive either 6 weeks of nicotine or placebo patch and were followed for one year. Throughout the study, lower total withdrawal score was associated with greater education (p = 0.044), older age of smoking initiation (p = 0.017), lower nicotine dependence (p = 0.024), higher confidence in ability to quit (p = 0.020), lower reported depression (p < 0.001), higher adherence to patch (p = 0.026), belief of receiving nicotine patches rather than placebo (p = 0.011), and waterpipe use (p = 0.047). Lower nicotine dependence, greater educational attainment, higher confidence in ability to quit and waterpipe use predict lower withdrawal severity. Waterpipe smoking may serve as a barrier to smoking cessation efforts in countries where its use is highly prevalent. Further, expectancies about the effects of pharmacotherapy appear to mediate the experience of nicotine withdrawal.

Sports Participation and Withdrawal: A Developmental Motivational Commentary.

ERIC Educational Resources Information Center

Hom, Larry L.

1996-01-01

Examines the nature of adolescents' sports involvement as reflected in reasons for participation and withdrawal. Claims that the degree of fun, the motivation to attain competence, and the capacity to distinguish ability from effort are important. Concludes that if the goal of sports is to foster a healthy lifestyle, the issue of maximizing…

Effect of electron withdrawing unit for dye-sensitized solar cell based on D-A-π-A organic dyes

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

Kwon, Dong Yuel; Chang, Dong Min; Kim, Young Sik, E-mail: youngkim@hongik.ac.kr

2014-10-15

Highlights: • To gain the red-shifted absorption spectra, withdrawing unit was substituted in dye. • By the introduction of additional withdrawing unit, LUMOs level of dye are decreased. • Decreasing LUMOs level of dye caused the red-shifted absorption spectra of dye. • Novel acceptor, DCRD, showed better photovoltaic properties than cyanoacetic acid. - Abstract: In this work, two novel D-A-π-A dye sensitizers with triarylamine as an electron donor, isoindigo and cyano group as electron withdrawing units and cyanoacetic acid and 2-(1,1-dicyanomethylene) rhodanine as an electron acceptor for an anchoring group (TICC, TICR) were designed and investigated with the ID6 dyemore » as the reference. The difference in HOMO and LUMO levels were compared according to the presence or absence of isoindigo in ID6 (TC and ID6). To gain insight into the factors responsible for photovoltaic performance, we used density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. Owing to different LUMO levels for each acceptor, the absorption band and molar extinction coefficient of each dye was different. Among the dyes, TICR showed more red-shifted and broader absorption spectra than other dyes and had a higher molar extinction coefficient than the reference. It is expected that TICR would show better photovoltaic properties than the other dyes, including the reference dye.« less

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study.

PubMed

Dostanić, J; Lončarević, D; Zlatar, M; Vlahović, F; Jovanović, D M

2016-10-05

A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31+G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σp constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO2 photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups. Copyright © 2016 Elsevier B.V. All rights reserved.

Elucidating the Structure-Reactivity Correlations of Phenothiazine-Based Fluorescent Probes toward ClO.

PubMed

Wang, Shichao; Zhang, Boyu; Wang, Wenjing; Feng, Gang; Yuan, Daqiang; Zhang, Xuanjun

2018-06-07

In this work, with the aim of developing effective molecular probes and investigating the structure-reactivity correlation, a short series of phenothiazine-based fluorescent probes are designed for the detection of ClO - with differing electron push-pull groups. Sensing experiment results and single-crystal X-ray analysis with the aid of time-dependent DFT (TD-DFT) calculations reveal that substituting groups with increasing electron-withdrawing ability can increase the dihedral angle of the phenothiazine moiety and reduce the gap energy of the probes, leading to enhanced reactivity toward ClO - . Both PT1 and PT2 show two-color switching upon detection of ClO - . PT1, with the strong electron-donating group thiophene, shows a fluorescence color switch from salmon to blue. PT2, with a medium electron-donating/accepting group benzothiazole, shows a fluorescence color switch from red to green. However, both PT1 and PT2 show almost no response to ONOO - . Through the introduction of strong electron-withdrawing ketone combined with a cyano group, PT3 shows a cyan emission upon detection of ClO - and weak red emission upon detection of ONOO - . HRMS and 1 H NMR results confirm that PT1 and PT2 have the same sensing mode, in which the divalent sulfur of phenothiazine can be oxidized to sulfoxide by ClO - . Upon reaction with ClO - , PT3 experiences two-step reactions. It is first oxidized into the sulfone structure by ClO - , and then transformed into sulfoxide phenothiazine aldehyde. Upon encountering ONOO - , PT3 changes into an aldehyde structure and some nonfluorescent byproducts. Owing to their special selectivity and high sensitivity, PT1 and PT2 are applied to image the endogenous ClO - in macrophage cells and zebrafish larvae. This study is expected to provide useful guidelines for probe design for various applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of cannabis and tobacco withdrawal: severity and contribution to relapse.

PubMed

Budney, Alan J; Vandrey, Ryan G; Hughes, John R; Thostenson, Jeff D; Bursac, Zoran

2008-12-01

This naturalistic telephone survey study compared perceptions of withdrawal severity in 67 daily cannabis users and 54 daily tobacco cigarette smokers who made quit attempts during the prior 30 days. A Withdrawal Symptom Checklist assessed the severity of abstinence symptoms and a Likert scale assessed perceived relations between abstinence symptoms and relapse. A composite Withdrawal Discomfort Score did not differ significantly between groups (M = 13.0 for cannabis, vs. M = 13.2 for tobacco). Individual symptom severity ratings were also of similar magnitude, except craving and sweating were slightly higher for tobacco. Both groups reported that withdrawal contributed substantially to relapse, and the strength of these ratings was similar across groups. The diverse convenience sample examined in this study adds external validity and generalizability to prior studies that included only users not planning to quit or excluded many common types of cannabis users. The comparable withdrawal experience from these heterogeneous cannabis and tobacco users supports previous findings from controlled laboratory studies and indicates that real-world, frequent cannabis users perceive that withdrawal symptoms negatively affect their desire and ability to quit.

Preparing Nursing and Social Work Students to Care for Patients in Acute Alcohol Withdrawal.

PubMed

Gates, Sharon A; Brown, James R

Alcohol and other drug abuse has become a national crisis with approximately 26% of general medical patients having alcohol-related problems. New nurses and social workers are often not prepared to care for patients with severe alcohol withdrawal symptoms because they lack experience in actual crisis situations. The purpose of this study was to prepare nursing and social work students to care for a patient undergoing an acute alcohol withdrawal process. Nine groups of 8-10 students participated in a 2.5-hour simulation event that included an alcohol withdrawal seizure, team meeting, and discharge of the patient. Students recognized the importance of all the professional roles and how each professional benefits patient care. Before the simulation, students thought they were prepared to care for patients experiencing alcohol withdrawal; however, the crisis of an alcohol seizure decreased the student's ability to perform skills and communicate effectively. These findings suggest that new nurses and social workers may not be prepared to care for the acute alcohol withdrawal patient.

Positron annihilation studies in solid substituted aromatic compounds

NASA Astrophysics Data System (ADS)

Oliveira, F. C.; Oliveira, A. M.; Donnici, C. L.; Machado, J. C.; Magalhães, W. F.; Windmöller, D.; Fulgêncio, F. H.; Souza, L. R.

2011-04-01

Positronium formation was investigated in benzene and naphthalene compounds with electron donating (sbnd NH2 and sbnd OH) and electron withdrawing (sbnd CN and sbnd NO2) substituents. The results exhibit an increase in the positronium formation yield whenever donating groups are bound to the ring and a decrease with withdrawing groups. These results can be attributed to the π-system electronic density variation in the aromatic ring. The amount of positronium obtained, I3 parameter, has been correlated with the Hammett (σ) and Brown-Okamoto (σp+) constants and adjusted through the modified Hammett equation, which employs the ratio I3/I3ϕ, yielding a satisfactory fit.

The excited-state intramolecular proton transfer in Nsbnd H-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight

NASA Astrophysics Data System (ADS)

Yuan, Huijuan; Feng, Songyan; Wen, Keke; Guo, Xugeng; Zhang, Jinglai

2018-02-01

Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)sbnd H ⋯ N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the Nsbnd S1 form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF3 group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)sbnd H ⋯ N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.

Stereotype Threat, Identification with Academics, and Withdrawal from School: Why the Most Successful Students of Colour Might Be Most Likely to Withdraw

ERIC Educational Resources Information Center

Osborne, Jason W.; Walker, Christopher

2006-01-01

Claude Steeles' stereotype threat hypothesis posits that when there are negative stereotypes about the intellectual capacity of certain (stigmatised) groups, members of that group suffer aversive consequences; group members who are most strongly identified with the stigmatised domain in question (e.g., intellectual or academic ability) are those…

Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

PubMed

Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

2016-09-01

The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

Application of Chan-Lam cross coupling for the synthesis of N-heterocyclic carbene precursors bearing strong electron donating or withdrawing groups

NASA Astrophysics Data System (ADS)

Huang, Liliang; He, Chengxiang; Sun, Zhihua

2015-07-01

Chan-Lam cross coupling allowed efficient synthesis of N,N’-disubstituted ortho-phenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with moderate to high yields. These diamines can then be turned into N-heterocyclic carbene precursors after condensation with trimethyl orthoformate. The same strategy can also be utilized for the synthesis of N-monosubstituted aniline derivatives containing a functionalized ortho-aminomethyl group as intermediates for chiral 6-membered ring carbene precursors.

Mitragynine Attenuates Withdrawal Syndrome in Morphine-Withdrawn Zebrafish

PubMed Central

Khor, Beng-Siang; Amar Jamil, Mohd Fadzly; Adenan, Mohamad Ilham; Chong Shu-Chien, Alexander

2011-01-01

A major obstacle in treating drug addiction is the severity of opiate withdrawal syndrome, which can lead to unwanted relapse. Mitragynine is the major alkaloid compound found in leaves of Mitragyna speciosa, a plant widely used by opiate addicts to mitigate the harshness of drug withdrawal. A series of experiments was conducted to investigate the effect of mitragynine on anxiety behavior, cortisol level and expression of stress pathway related genes in zebrafish undergoing morphine withdrawal phase. Adult zebrafish were subjected to two weeks chronic morphine exposure at 1.5 mg/L, followed by withdrawal for 24 hours prior to tests. Using the novel tank diving tests, we first showed that morphine-withdrawn zebrafish display anxiety-related swimming behaviors such as decreased exploratory behavior and increased erratic movement. Morphine withdrawal also elevated whole-body cortisol levels, which confirms the phenotypic stress-like behaviors. Exposing morphine-withdrawn fish to mitragynine however attenuates majority of the stress-related swimming behaviors and concomitantly lower whole-body cortisol level. Using real-time PCR gene expression analysis, we also showed that mitragynine reduces the mRNA expression of corticotropin releasing factor receptors and prodynorphin in zebrafish brain during morphine withdrawal phase, revealing for the first time a possible link between mitragynine's ability to attenuate anxiety during opiate withdrawal with the stress-related corticotropin pathway. PMID:22205946

A Short-Term, Multicenter, Placebo-Controlled, Randomized Withdrawal Study of a Metabotropic Glutamate 2/3 Receptor Agonist Using an Electronic Patient-Reported Outcome Device in Patients With Schizophrenia

PubMed Central

Stauffer, Virginia L.; Baygani, Simin K.; Kinon, Bruce J.; Krikke-Workel, Judith O.

2014-01-01

Abstract This 6-week, multicenter, randomized withdrawal, placebo-controlled trial sought to determine whether symptoms of physical dependence occur after abrupt cessation of pomaglumetad methionil (LY2140023 monohydrate), a metabotropic glutamate 2/3 receptor agonist, in patients with schizophrenia. Eligible outpatients, 18 to 65 years old who required a modification or initiation of antipsychotic medication received 4 weeks of pomaglumetad methionil during open-label treatment and then were randomized, double-blind, to continue pomaglumetad methionil or receive placebo for 2 weeks. The primary outcome compared results of the 3-day moving mean of the total score on the Discontinuation Symptom Checklist-Modified Rickels for pomaglumetad methionil-treated patients with those on placebo during the randomized withdrawal phase. An electronic patient-reported outcome (ePRO) device was used daily to record these results. During the withdrawal phase, 103 patients were randomized, and 98 patients completed the trial. There was no statistically significant evidence of withdrawal symptoms associated with placebo compared with pomaglumetad methionil continuation as measured by Discontinuation Symptom Checklist-Modified Rickels (P = 0.170). The results are supported by secondary analyses with the clinician-rated, Clinical Institute Withdrawal Assessment of Alcohol Scale Revised, which showed no statistically significant differences between treatment groups. Using the ePRO device, 82.5% of the patients achieved 75% to 100% of compliance. No discontinuations due to worsening of schizophrenia, serious adverse events, deaths, or seizures were reported during either phase of the study. These findings suggest that there is no evidence of withdrawal symptoms associated with the abrupt discontinuation of pomaglumetad methionil and that an ePRO device can be successfully used in a multicenter schizophrenia trial. PMID:25006819

The comparative efficacy of first- versus second-generation electronic cigarettes in reducing symptoms of nicotine withdrawal.

PubMed

Lechner, William V; Meier, Ellen; Wiener, Josh L; Grant, DeMond M; Gilmore, Jenna; Judah, Matt R; Mills, Adam C; Wagener, Theodore L

2015-05-01

Currently, electronic cigarettes (e-cigarettes) are studied as though they are a homogeneous category. However, there are several noteworthy differences in the products that fall under this name, including potential differences in the efficacy of these products as smoking cessation aids. The current study examined the comparative efficacy of first- and second-generation e-cigarettes in reducing nicotine withdrawal symptoms in a sample of current smokers with little or no experience of using e-cigarettes. Twenty-two mildly to moderately nicotine-dependent individuals were randomized to a cross-over design in which they used first- and second-generation e-cigarettes on separate days with assessment of withdrawal symptoms directly prior to and after product use. A community-based sample recruited in the Midwest region of the United States reported a mean age of 28.6 [standard deviation (SD) = 12.9]. The majority were male (56.5%), Caucasian (91.3%), reported smoking an average of 15.2 (SD = 9.6) tobacco cigarettes per day, and a mean baseline carbon monoxide (CO) level of 18.7 parts per million (p.p.m.). Symptoms of withdrawal from nicotine were measured via the Mood and Physical Symptoms Scale. Analysis of changes in withdrawal symptoms revealed a significant time × product interaction F(1, 21)  = 5.057, P = 0.036, n(2) P  = 0.202. Participants experienced a larger reduction in symptoms of nicotine withdrawal after using second-generation compared with first-generation e-cigarettes. Second-generation e-cigarettes seem to be more effective in reducing symptoms of nicotine withdrawal than do first-generation e-cigarettes. © 2015 Society for the Study of Addiction.

Social Withdrawal Behaviour at One Year of Age Is Associated with Delays in Reaching Language Milestones in the EDEN Mother-Child Cohort Study.

PubMed

Guedeney, Antoine; Forhan, Anne; Larroque, Beatrice; de Agostini, Maria; Pingault, Jean-Baptiste; Heude, Barbara

2016-01-01

The aim of the study was to examine the relationship between social withdrawal behaviour at one year and motor and language milestones. One-year old children from the EDEN French population-based birth cohort study (Study on the pre- and postnatal determinants of the child's development and prospective health Birth Cohort Study) were included. Social withdrawal at one year was assessed by trained midwives using the Alarm Distress BaBy (ADBB) scale. Midwives concurrently examined infants' motor and language milestones. Parents reported on child's psychomotor and language milestones, during the interview with the midwife. After adjusting for potential confounding factors, social withdrawal behaviour was significantly associated with concurrent delays in motor and language milestones assessed by the midwife or the parents. Higher scores on social withdrawal behaviour as assessed with the ADBB were associated with delays in reaching language milestones, and to a lesser extent with lower motor ability scores. Taking the contribution of social withdrawal behaviour into account may help understand the unfolding of developmental difficulties in children.

Synthesis and Photoluminescent Properties of Arylethynyl substituted 9,10-Anthraquinones

NASA Technical Reports Server (NTRS)

Yang, Jin-Hua; Dass, Amala; Sotiriou-Leventis, Chariklia; Leventis, Nicholas

2003-01-01

A series of arylethynyl substituted anthraquinones were synthesized via Sonogashira coupling reactions of 2,7- dibromo-, 2,6-dibromo- and 2-bromoanthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants for electron donating and electron withdrawing groups separately. All compounds are photoluminescent both in solution (quantum yield of emission approximately 2%) and as solids. X-ray crystallographic characterization of 2,7-bisphenylethynyl anthraquinone indicates a monoclinic p2(l/n) space group and no indication for pi-overlap that would promote self-quenching. The emission maxima are red- shifted by both electron donating and electron withdrawing groups alike. The Stokes shifts of all compounds are significant and are correlated to the electronic properties of the substituents. The reduced forms of these compounds are also photoluminescent and the emission originates from the dihydroanthraquinone core.

Hyperpolarizable compounds and devices fabricated therefrom

DOEpatents

Therien, Michael J.; DiMagno, Stephen G.

1998-01-01

Substituted compounds having relatively large molecular first order hyperpolarizabilities are provided, along with devices and materials containing them. In general, the compounds bear electron-donating and electron-withdrawing chemical substituents on a polyheterocyclic core.

The synthesis and characterization of azocalix[4]arene based chemosensors and investigation of their properties

NASA Astrophysics Data System (ADS)

Elçin, Serkan; Çılgı, Gülbanu Koyundereli; Bayrakdar, Alpaslan; Deligöz, Hasalettin

2015-05-01

In the present study, azocalix[4]arenes were prepared by linking 4-methoxy, 4-methyl, 4-ethyl, 4-chloro, 4-bromo and 4-nitroaniline to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arene tetraester derivatives, (4a-f), have been prepared with the incorporation of ethyl ester units to azocalix[4]arene. Characterization of the synthesized azocalix[4]arenes was carried using elemental analyses, UV-vis, FT-IR and 1H NMR spectroscopic techniques. The effect of varying pH levels and solvent types on the absorption ability of azocalix[n]arenes substituted with electron-donating and electron-withdrawing groups was examined. Thermal decomposition of azocalix[4]arene derivatives (4a-f) was investigated by means of thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) analyses. In conclusion of the examination of the extraction we found a selectivity characteristic of these compounds toward Ag+, Hg+ and Hg2+ cations.

Optimizing withdrawal from drinking water reservoirs to reduce downstream temperature pollution and reservoir hypoxia.

PubMed

Weber, M; Rinke, K; Hipsey, M R; Boehrer, B

2017-07-15

Sustainable management of drinking water reservoirs requires balancing the demands of water supply whilst minimizing environmental impact. This study numerically simulates the effect of an improved withdrawal scheme designed to alleviate the temperature pollution downstream of a reservoir. The aim was to identify an optimal withdrawal strategy such that water of a desirable discharge temperature can be supplied downstream without leading to unacceptably low oxygen concentrations within the reservoir. First, we calibrated a one-dimensional numerical model for hydrodynamics and oxygen dynamics (GLM-AED2), verifying that the model reproduced water temperatures and hypolimnetic dissolved oxygen concentrations accurately over a 5 year period. Second, the model was extended to include an adaptive withdrawal functionality, allowing for a prescribed withdrawal temperature to be found, with the potential constraint of hypolimnetic oxygen concentration. Scenario simulations on epi-/metalimnetic withdrawal demonstrate that the model is able to autonomously determine the best withdrawal height depending on the thermal structure and the hypolimnetic oxygen concentration thereby optimizing the ability to supply a desirable discharge temperature to the downstream river during summer. This new withdrawal strategy also increased the hypolimnetic raw water volume to be used for drinking water supply, but reduced the dissolved oxygen concentrations in the deep and cold water layers (hypolimnion). Implications of the results for reservoir management are discussed and the numerical model is provided for operators as a simple and efficient tool for optimizing the withdrawal strategy within different reservoir contexts. Copyright © 2017 Elsevier Ltd. All rights reserved.

Substituents on Quinone Methides Strongly Modulate Formation and Stability of Their Nucleophilic Adducts

PubMed Central

Weinert, Emily E.; Dondi, Ruggero; Colloredo-Melz, Stefano; Frankenfield, Kristen N.; Mitchell, Charles H.; Freccero, Mauro; Rokita, Steven E.

2008-01-01

Electronic perturbation of quinone methides (QM) greatly influences their stability and in turn alters the kinetics and product profile of QM reaction with deoxynucleosides. Consistent with the electron deficient nature of this reactive intermediate, electron-donating substituents are stabilizing and electron-withdrawing substituents are destabilizing. For example, a dC N3-QM adduct is made stable over the course of observation (7 days) by the presence of an electron-withdrawing ester group that inhibits QM regeneration. Conversely, a related adduct with an electron donating methyl group is very labile and regenerates its QM with a half-life of approximately 5 hr. The generality of these effects is demonstrated with a series of alternative quinone methide precursors (QMP) containing a variety of substituents attached at different positions with respect to the exocyclic methylene. The rates of nucleophilic addition to substituted QMs measured by laser flash photolysis similarly span five orders of magnitude with electron rich species reacting most slowly and electron deficient species reacting most quickly. The reversibility of QM reaction can now be predictably adjusted for any desired application. PMID:16953635

Sex Differences in Acute Ethanol Withdrawal Severity After Adrenalectomy and Gonadectomy in WSP and WSR Mice

PubMed Central

Strong, Moriah N.; Kaufman, Katherine R.; Crabbe, John C.; Finn, Deborah A.

2009-01-01

Recent findings suggest that the ability of ethanol (EtOH) to increase the levels of neurosteroids with potent γ-aminobutyric acid (GABA)ergic properties can influence measures of EtOH sensitivity. Earlier studies determined that removal of the adrenals and gonads diminished the steroidogenic effect of EtOH and significantly increased acute EtOH withdrawal severity in two inbred mouse strains that differed in withdrawal severity, suggesting the contribution of anticonvulsant GABAergic steroids to acute withdrawal in intact animals. Thus, the goal of the present studies was to investigate the consequence of steroid removal on acute EtOH withdrawal through excision of the adrenals and gonads, in another genetic animal model of EtOH withdrawal differences, the Withdrawal Seizure-Prone (WSP) and -Resistant (WSR) selected lines. Male and female WSP and WSR mice underwent surgical removal of the adrenals and gonads or no organ removal (SHAM). One to two weeks later, baseline handling-induced convulsions (HICs) were assessed, mice were given a 4 g/kg dose of ethanol, and HICs were measured hourly for 12 hours and then at 24 hours. The combination surgery significantly increased EtOH withdrawal in WSP and WSR female mice, as measured by area under the curve (AUC) and peak HIC scores. AUC was significantly positively correlated with plasma corticosterone levels and significantly negatively correlated with progesterone levels. In contrast, surgical status did not alter withdrawal severity in male WSP and WSR mice. Overall, the increase in acute ethanol withdrawal severity in female WSP and WSR mice following adrenalectomy and gonadectomy corroborate our recent evidence that withdrawal from a high dose of EtOH can be modulated by anticonvulsant steroids produced in the periphery. PMID:19671463

Hyperpolarizable compounds and devices fabricated therefrom

DOEpatents

Therien, M.J.; DiMagno, S.G.

1998-07-21

Substituted compounds having relatively large molecular first order hyperpolarizabilities are provided, along with devices and materials containing them. In general, the compounds bear electron-donating and electron-withdrawing chemical substituents on a polyheterocyclic core. 13 figs.

Evaluation of the appropriate use of a CIWA-Ar alcohol withdrawal protocol in the general hospital setting.

PubMed

Eloma, Amanda S; Tucciarone, Jason M; Hayes, Edmund M; Bronson, Brian D

2018-01-01

The Clinical Institute Withdrawal Assessment-Alcohol, Revised (CIWA-Ar) is an assessment tool used to quantify alcohol withdrawal syndrome (AWS) severity and inform benzodiazepine treatment for alcohol withdrawal. To evaluate the prescribing patterns and appropriate use of the CIWA-Ar protocol in a general hospital setting, as determined by the presence or absence of documented AWS risk factors, patients' ability to communicate, and provider awareness of the CIWA-Ar order. This retrospective chart review included 118 encounters of hospitalized patients placed on a CIWA-Ar protocol during one year. The following data were collected for each encounter: patient demographics, admitting diagnosis, ability to communicate, and admission blood alcohol level; and medical specialty of the clinician ordering CIWA-Ar, documentation of the presence or absence of established AWS risk factors, specific parameters of the protocol ordered, service admitted to, provider documentation of awareness of the active protocol within 48 h of initial order, total benzodiazepine dose equivalents administered and associated adverse events. 57% of patients who started on a CIWA-Ar protocol had either zero or one documented risk factor for AWS (19% and 38% respectively). 20% had no documentation of recent alcohol use. 14% were unable to communicate. 19% of medical records lacked documentation of provider awareness of the ordered protocol. Benzodiazepine associated adverse events were documented in 15% of encounters. The judicious use of CIWA-Ar protocols in general hospitals requires mechanisms to ensure assessment of validated alcohol withdrawal risk factors, exclusion of patients who cannot communicate, and continuity of care during transitions.

The Power of Stories: Facilitating Social Communication in Children with Limited Language Abilities

ERIC Educational Resources Information Center

Brinton, Bonnie; Fujiki, Martin

2017-01-01

Children with limited language expression and comprehension abilities are at risk for academic failure, particularly in literacy acquisition. In addition, these children often have poor social outcomes, including difficulty forming friendships, social exclusion, withdrawal, and victimization. The academic and social difficulties that these…

Social Withdrawal Behaviour at One Year of Age Is Associated with Delays in Reaching Language Milestones in the EDEN Mother-Child Cohort Study

PubMed Central

Guedeney, Antoine; Forhan, Anne; de Agostini, Maria; Pingault, Jean-Baptiste; Heude, Barbara

2016-01-01

Objective The aim of the study was to examine the relationship between social withdrawal behaviour at one year and motor and language milestones. Materials and Methods One-year old children from the EDEN French population-based birth cohort study (Study on the pre- and postnatal determinants of the child’s development and prospective health Birth Cohort Study) were included. Social withdrawal at one year was assessed by trained midwives using the Alarm Distress BaBy (ADBB) scale. Midwives concurrently examined infants’ motor and language milestones. Parents reported on child’s psychomotor and language milestones, during the interview with the midwife. Results After adjusting for potential confounding factors, social withdrawal behaviour was significantly associated with concurrent delays in motor and language milestones assessed by the midwife or the parents. Discussion Higher scores on social withdrawal behaviour as assessed with the ADBB were associated with delays in reaching language milestones, and to a lesser extent with lower motor ability scores. Taking the contribution of social withdrawal behaviour into account may help understand the unfolding of developmental difficulties in children. PMID:27391482

Molecular Engineering of UV/Vis Light-Emitting Diode (LED)-Sensitive Donor-π-Acceptor-Type Sulfonium Salt Photoacid Generators: Design, Synthesis, and Study of Photochemical and Photophysical Properties.

PubMed

Wu, Xingyu; Jin, Ming; Xie, Jianchao; Malval, Jean-Pierre; Wan, Decheng

2017-11-07

A series of donor-π-acceptor-type sulfonium salt photoacid generators (PAGs) were designed and synthesized by systematically changing electron-donating groups, π-conjugated systems, electron-withdrawing groups, and the number of branches through molecular engineering. These PAGs can effectively decompose under UV/Vis irradiation from a light-emitting diode (LED) light source because of the matching absorption and emitting spectra of the LEDs. The absorption and acid-generation properties of these sulfonium salts were elucidated by UV/Vis spectroscopy and so forth. Results indicated that the PAG performance benefited from the introduction of strong electron-donating groups, specific π-conjugated structures, certain electron-withdrawing groups, or two-branched structures. Most sulfonium salts showed potential as photoinitiators under irradiation by a wide variety of UV and visible LEDs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measuring Changes in Tactile Sensitivity in the Hind Paw of Mice Using an Electronic von Frey Apparatus

PubMed Central

Martinov, Tijana; Mack, Madison; Sykes, Akilah; Chatterjea, Devavani

2013-01-01

Measuring inflammation-induced changes in thresholds of hind paw withdrawal from mechanical pressure is a useful technique to assess changes in pain perception in rodents. Withdrawal thresholds can be measured first at baseline and then following drug, venom, injury, allergen, or otherwise evoked inflammation by applying an accurate force on very specific areas of the skin. An electronic von Frey apparatus allows precise assessment of mouse hind paw withdrawal thresholds that are not limited by the available filament sizes in contrast to classical von Frey measurements. The ease and rapidity of measurements allow for incorporation of assessment of tactile sensitivity outcomes in diverse models of rapid-onset inflammatory and neuropathic pain as multiple measurements can be taken within a short time period. Experimental measurements for individual rodent subjects can be internally controlled against individual baseline responses and exclusion criteria easily established to standardize baseline responses within and across experimental groups. Thus, measurements using an electronic von Frey apparatus represent a useful modification of the well-established classical von Frey filament-based assays for rodent mechanical allodynia that may also be applied to other nonhuman mammalian models. PMID:24378519

Estimating Monthly Water Withdrawals, Return Flow, and Consumptive Use in the Great Lakes Basin

USGS Publications Warehouse

Shaffer, Kimberly H.; Stenback, Rosemary S.

2010-01-01

Water-resource managers and planners require water-withdrawal, return-flow, and consumptive-use data to understand how anthropogenic (human) water use affects the hydrologic system. Water models like MODFLOW and GSFLOW use calculations and input values (including water-withdrawal and return flow data) to simulate and predict the effects of water use on aquifer and stream conditions. Accurate assessments of consumptive use, interbasin transfer, and areas that are on public supply or sewer are essential in estimating the withdrawal and return-flow data needed for the models. As the applicability of a model to real situations depends on accurate input data, limited or poor water-use data hampers the ability of modelers to simulate and predict hydrologic conditions. Substantial differences exist among the many agencies nationwide that are responsible for compiling water-use data including what data are collected, how the data are organized, how often the data are collected, quality assurance, required level of accuracy, and when data are released to the public. This poster presents water-use information and estimation methods summarized from recent U.S. Geological Survey (USGS) reports with the intent to assist water-resource managers and planners who need estimates of monthly water withdrawals, return flows, and consumptive use. This poster lists references used in Shaffer (2009) for water withdrawals, consumptive use, and return flows. Monthly percent of annual withdrawals and monthly consumptive-use coefficients are used to compute monthly water withdrawals, consumptive use, and return flow for the Great Lakes Basin.

Organic sensitizers from D-π-A to D-A-π-A: effect of the internal electron-withdrawing units on molecular absorption, energy levels and photovoltaic performances.

PubMed

Wu, Yongzhen; Zhu, Weihong

2013-03-07

The high performance and low cost of dye-sensitized solar cells (DSSCs) have drawn great interest from both academic and industrial circles. The research on exploring novel efficient sensitizers, especially on inexpensive metal-free pure organic dyes, has never been suspended. The donor-π bridge-acceptor (D-π-A) configuration is mainstream in the design of organic sensitizers due to its convenient modulation of the intramolecular charge-transfer nature. Recently, it has been found that incorporation of additional electron-withdrawing units (such as benzothiadiazole, benzotriazole, quinoxaline, phthalimide, diketopyrrolopyrrole, thienopyrazine, thiazole, triazine, cyanovinyl, cyano- and fluoro-substituted phenyl) into the π bridge as internal acceptors, termed the D-A-π-A configuration, displays several advantages such as tuning of the molecular energy levels, red-shift of the charge-transfer absorption band, and distinct improvement of photovoltaic performance and stability. We apply the D-A-π-A concept broadly to the organic sensitizers containing additional electron-withdrawing units between electron donors and acceptors. This review is projected to summarize the category of pure organic sensitizers on the basis of the D-A-π-A feature. By comparing the structure-property relationship of typical photovoltaic D-A-π-A dyes, the important guidelines in the design of such materials are highlighted.

The effect of the ecstasy 'come-down' on the diagnosis of ecstasy dependence.

PubMed

McKetin, Rebecca; Copeland, Jan; Norberg, Melissa M; Bruno, Raimondo; Hides, Leanne; Khawar, Laila

2014-06-01

The existence of an ecstasy-dependence syndrome is controversial. We examined whether the acute after-effects of ecstasy use (i.e. the 'come-down') falsely lead to the identification of ecstasy withdrawal and the subsequent diagnosis of ecstasy dependence. The Structured Clinical Interview for DSM-IV-TR Disorders: Research Version (SCID-RV) was administered to 214 Australian ecstasy users. Ecstasy withdrawal was operationalised in three contrasting ways: (i) as per DSM-IV criteria; (ii) as the expected after-effects of ecstasy (a regular come-down); or (iii) as a substantially greater or longer come-down than on first use (intense come-down). These definitions were validated against frequency of ecstasy use, readiness to change and ability to resist the urge to use ecstasy. Confirmatory factor analyses were used to see how they aligned with the overall dependence syndrome. Come-down symptoms increased the prevalence of withdrawal from 1% (DSM-IV criterion) to 11% (intense come-downs) and 75% (regular come-downs). Past year ecstasy dependence remained at 31% when including the DSM-IV withdrawal criteria and was 32% with intense come-downs, but increased to 45% with regular come-downs. Intense come-downs were associated with lower ability to resist ecstasy use and loaded positively on the dependence syndrome. Regular come-downs did not load positively on the ecstasy-dependence syndrome and were not related to other indices of dependence. The acute after-effects of ecstasy should be excluded when assessing ecstasy withdrawal as they can lead to a false diagnosis of ecstasy dependence. Worsening of the ecstasy come-down may be a marker for dependence. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Drug withdrawal conceptualized as a stressor

PubMed Central

Chartoff, Elena H.; Carlezon, William A.

2015-01-01

Drug withdrawal is often conceptualized as an aversive state that motivates drug-seeking and drug-taking behaviors in humans. Stress is more difficult to define, but is also frequently associated with aversive states. Here we describe evidence for the simple theory that drug withdrawal is a stress-like state, on the basis of common effects on behavioral, neurochemical, and molecular endpoints. We also describe data suggesting a more complex relationship between drug withdrawal and stress. As one example, we will highlight evidence that, depending on drug class, components of withdrawal can produce effects that have characteristics consistent with mood elevation. In addition, some stressors can act as positive reinforcers, defined as having the ability to increase the probability of a behavior that produces it. As such, accumulating evidence supports the general principles of opponent process theory, whereby processes that have an affective valence are followed in time by an opponent process that has the opposite valence. Throughout, we identify gaps in knowledge and propose future directions for research. A better understanding of the similarities, differences, and overlaps between drug withdrawal and stress will lead to the development of improved treatments for addiction, as well as for a vast array of neuropsychiatric conditions that are triggered or exacerbated by stress. PMID:25083570

Theoretical and Experimental: The Synthetic and Anion-Binding Properties of Tripodal Salicylaldehyde Derivatives.

PubMed

Xu, Zhong-Jie; Zhang, Li-Rong

2016-05-19

A series of colorimetric anion probes 1-6 containing OH and NO₂ groups were synthesized, and their recognition properties toward various anions were investigated by visual observation, ultraviolet-visible spectroscopy, fluorescence, ¹H nuclear magnetic resonance titration spectra and theoretical investigation. Nanomaterials of three compounds 2-4 were prepared successfully. Four compounds 3-6 that contain electron-withdrawing substituents showed a high binding ability for AcO(-). The host-guest complex formed through a 1:1 binding ratio, and color changes were detectable during the recognition process. Theoretical investigation analysis revealed that an intramolecular hydrogen bond existed in the structures of compounds and the roles of molecular frontier orbitals in molecular interplay. These studies suggested that this series of compounds could be used as colorimetric probes to detect of AcO(-).

Palladium-Catalyzed Arylation of Fluoroalkylamines

PubMed Central

Brusoe, Andrew T.; Hartwig, John F.

2015-01-01

We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

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

The effects of e-cigarette visual appearance on craving and withdrawal symptoms in abstinent smokers.

PubMed

Dawkins, Lynne; Munafò, Marcus; Christoforou, Gina; Olumegbon, Naomi; Soar, Kirstie

2016-02-01

Electronic cigarette (e-cigarette) use is becoming increasing popular among smokers, and there is a plethora of devices available. Nicotine delivery is clearly important for reducing tobacco craving and withdrawal symptoms, but other sensorimotor aspects of e-cigarettes (such as visual appearance) may contribute to this effect. This study explored whether it is important for an e-cigarette to visually resemble a tobacco cigarette in order to reduce craving and withdrawal symptoms. Sixty-three cigarette smokers (40% female, aged 18-65 years) who were not current e-cigarette users were randomly allocated to take ten 3-s puffs from either a white or a red first-generation e-cigarette following overnight abstinence. Current craving (urge to smoke) and nicotine withdrawal symptoms (using the Mood and Physical Symptoms Scale [MPSS]) were measured before and 10 min after use. Linear regression revealed higher craving and withdrawal symptoms in the red condition versus the white condition, but only among those who were e-cigarette naive (craving: B = .76, p = .009; withdrawal symptoms: B = 2.18, p = .009), not among those with e-cigarette experience (craving: B = -.08, p = .89; withdrawal symptoms: B = .24, p = .81), and these effects differed between groups (p = .04 and 0.01 for craving and withdrawal symptoms, respectively). In conclusion, cigarette-like appearance was associated with lower craving and withdrawal symptoms, but only for those with no prior e-cigarette experience. This effect, putatively mediated via classical conditioning or expectancies, may aid understanding of smokers' initial preferences for "cigalike" e-cigarette devices. (c) 2016 APA, all rights reserved).

Caffeine Withdrawal and Dependence: A Convenience Survey Among Addiction Professionals.

PubMed

Budney, Alan J; Brown, Pamela C; Griffiths, Roland R; Hughes, John R; Juliano, Laura M

2013-06-01

Caffeine withdrawal was included in the research appendix of the DSM-IV to encourage additional research to assist with determining its status for the next version of the manual. Caffeine dependence was not included because of a lack of empirical research at the time of publication. This study assessed the beliefs of addiction professionals about the clinical importance of caffeine withdrawal and dependence. A 6-item survey was developed and delivered electronically to the members of six professional organizations that focus on addiction. Open-ended comments were also solicited. Five hundred members responded. The majority (95%) thought that cessation of caffeine could produce a withdrawal syndrome, and that caffeine withdrawal can have clinical importance (73%); however, only half (48%) thought that caffeine withdrawal should be included in the Diagnostic and Statistical Manual of Mental Disorders (DSM). A majority (58%) believed that some people develop caffeine dependence; however, only 44% indicated that it should be in the DSM. Comments suggested that trepidation about inclusion of caffeine diagnoses was due to the concerns about the field of psychiatry being criticized for including common disorders with a relatively low clinical severity. Others, however, expressed an urgent need to take caffeine-related problems more seriously. The majority of addiction professionals believe that caffeine withdrawal and dependence disorders exist and are clinically important; however, these professionals are divided in whether caffeine withdrawal and dependence should be included in DSM. Wider dissemination of the extant literature on caffeine withdrawal and additional research on caffeine dependence will be needed to provide additional guidance to policymakers and healthcare workers.

Online exclusive: behavioral adjustment of children and adolescents with cancer: teacher, parent, and self-report.

PubMed

Moore, Ida M; Challinor, Julia; Pasvogel, Alice; Matthay, Katherine; Hutter, John; Kaemingk, Kris

2003-01-01

To describe behavioral adjustment in children and adolescents with acute lymphoblastic leukemia (ALL) and to determine whether behavioral adjustment is correlated with cognitive and academic abilities. Descriptive, cross-sectional design. Two pediatric oncology treatment centers. 47 children and adolescents who had been receiving ALL therapy for at least one year or who were off therapy for no more than three years and their parents and teachers. Wechsler Intelligence Scale for Children-Revised (WISC-R) and Wide Range Achievement Test-Revised (WRAT-R) data were available on a subset of 17 subjects. Parent, teacher, and self-report Behavioral Assessment System for Children (BASC) ratings were used to measure behavioral adjustment. WISC-R measured cognitive abilities, and WRAT-R measured academic abilities. Demographic, family, and treatment-related data also were collected. Behavioral adjustment and cognitive and academic abilities. At least 20% of teacher ratings for somatization, learning problems, leadership, and study skills; parent ratings for somatization, adaptability, attention problems, withdrawal, anxiety, social skills, and depression; and self-report ratings for anxiety and attitude to school were in the at-risk range (i.e., presence of significant problems that require treatment). The majority of teacher BASC ratings were correlated significantly with WISC-R and WRAT-R scores. Self-report depression and social stress ratings were correlated significantly with some WISC-R and WRAT-R scores. Treatment-related experiences such as body image alterations and mental and emotional problems were associated with problematic behaviors, including depression, somatization, withdrawal, and social stress. Youth with ALL are at risk for some behavioral adjustment problems, particularly anxiety, somatization, adaptability, attention, and withdrawal. Cognitive and academic abilities are associated with some dimensions of behavioral adjustment. Findings suggest the need for ongoing assessment of behavioral adjustment and cognitive and academic abilities of children with ALL. Behavioral interventions that target at-risk mannerisms, such as somatization, depression, anxiety, and social stress, are needed. Central nervous system treatment may contribute to behavioral adjustment problems, as well as to cognitive and academic problems. Strategies to improve academic abilities also may have a positive effect on behavioral adjustment.

Galanin and addiction.

PubMed

Picciotto, M R

2008-06-01

There has been increasing interest in the ability of neuropeptides involved in feeding to modulate circuits important for responses to drugs of abuse. A number of peptides with effects on hypothalamic function also modulate the mesolimbic dopamine system (ventral tegmental area and nucleus accumbens). Similarly, common stress-related pathways can modulate food intake, drug reward and symptoms of drug withdrawal. Galanin promotes food intake and the analgesic properties of opiates; thus it initially seemed possible that galanin might potentiate opiate reinforcement. Instead, galanin agonists decrease opiate reward, measured by conditioned place preference, and opiate withdrawal signs, whereas opiate reward and withdrawal are increased in knock-out mice lacking galanin. This is consistent with studies showing that galanin decreases activity-evoked dopamine release in striatal slices and decreases the firing rate of noradrenergic neurons in locus coeruleus, areas involved in drug reward and withdrawal, respectively. These data suggest that polymorphisms in genes encoding galanin or galanin receptors might be associated with susceptibility to opiate abuse. Further, galanin receptors might be potential targets for development of novel treatments for addiction.

Tuning the structural and electronic properties of novel thiophene-pyrrole based 1,2,3,4-tetrazine

NASA Astrophysics Data System (ADS)

Dutta, Rakesh; Kalita, Dhruba Jyoti

2017-04-01

Here, we have studied the structural and optoelectronic behaviour of a series of conjugated heterocyclic polymers. The basic monomer unit of the conjugated polymers contains a backbone of novel thiophene and pyrrole based 1,2,3,4-tetrazine. The other oligomers are designed by substituting the basic monomer unit with different electron-donating and electron-withdrawing groups at the nitrogen and the 3rd C-atom of the pyrrole and the thiophene ring respectively. We have calculated dihedral angles, HOMO-LUMO gaps, excitation energies and oscillator strengths by employing TD-DFT method. Our study reveals that compounds having bulky substituents exhibit larger dihedral angles. This in turn renders an increase in the band gaps (ΔH - L). Presence of the electron-withdrawing substituents also increases the ΔH - L values of the oligomers. However, the electron-donating groups decrease the ΔH - L values of the oligomers. Therefore, small electron-donating substituents have an overwhelming effect on the optoelectronic properties of the conjugated polymers which in turn makes them interesting materials with good conduction properties for fabrication of optoelectronic devices such as OLEDs, OFETs and solar cells.

Neighbouring group processes in the deamination of protonated phenylalanine derivatives.

PubMed

Lioe, Hadi; O'Hair, Richard A J

2005-10-21

The gas-phase fragmentation of protonated phenylalanine and a series of its derivatives (tyrosine, 4-methylphenylalanine, 4-aminophenylalanine, 4-methoxyphenylalanine, 4-tert-butylphenylalanine, 4-fluorophenylalanine, 4-chlorophenylalanine, 4-bromophenylalanine, 4-iodophenylalanine, 4-cyanophenylalanine, 4-nitrophenylalanine, 3-fluorophenylalanine, and 3,4-dichlorophenylalanine) were examined using a combination of low energy CID in a quadrupole ion trap mass spectrometer as well as DFT calculations and RRKM modelling. In particular, the relationship between the electron-donating ability of the substituent and the competitive losses of H2O + CO and NH3 were explored through the application of the Hammett equation. It was found that electron-donating substituents promote the loss of NH3, while electron-withdrawing substituents suppress the loss of NH3 and favour the H2O + CO loss fragmentation channel instead. These observations are consistent with a neighbouring group pathway operating for the loss of NH3. Molecular orbital calculation (at the B3LYP/6-31+G(d,p) level of theory) were also performed for a range of derivatives to compare the relative transition state energy barriers for three competing mechanisms: (i) the combined loss of H2O + CO, which is triggered by an initial intramolecular proton transfer from the ammonium group to hydroxyl OH, followed by the combined loss of H2O and CO to form an immonium ion; (ii) loss of NH3 via an aryl assisted neighbouring group pathway to yield a phenonium ion; (iii) loss of NH3 via a 1,2-hydride migration process, which results in the formation of a benzyl cation. The relative energy barriers for H2O + CO loss remain nearly constant, while that for both NH3 pathways increase as the substituent moves from electron-donating to electron-withdrawing. The relative transition state energy for loss of NH3 via the aryl assisted neighbouring group pathway is always lower than that of the 1,2-hydride migration process. RRKM modelling of the DFT predicted barrier heights suggest that the rate constants for H2O + CO loss are insensitive to the substituent on the ring, while the NH3 loss channels are greatly affected by the substituent. These theoretical results are consistent with the experimental observation of the relative yields of the competing fragmentation channels. Finally, comparisons with published gas phase and condensed phase studies on related systems are made.

Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes.

PubMed

Travia, Nicholas E; Xu, Zhenggang; Keith, Jason M; Ison, Elon A; Fanwick, Phillip E; Hall, Michael B; Abu-Omar, Mahdi M

2011-10-17

The cationic oxorhenium(V) complex [Re(O)(hoz)(2)(CH(3)CN)][B(C(6)F(5))(4)] [1; Hhoz = 2-(2'-hydroxyphenyl)-2-oxazoline] reacts with aryl azides (N(3)Ar) to give cationic cis-rhenium(VII) oxoimido complexes of the general formula [Re(O)(NAr)(hoz)(2)][B(C(6)F(5))(4)] [2a-2f; Ar = 4-methoxyphenyl, 4-methylphenyl, phenyl, 3-methoxyphenyl, 4-chlorophenyl, and 4-(trifluoromethyl)phenyl]. The kinetics of formation of 2 in CH(3)CN are first-order in both azide (N(3)Ar) and oxorhenium(V) complex 1, with second-order rate constants ranging from 3.5 × 10(-2) to 1.7 × 10(-1) M(-1) s(-1). A strong inductive effect is observed for electron-withdrawing substituents, leading to a negative Hammett reaction constant ρ = -1.3. However, electron-donating substituents on phenyl azide deviate significantly from this trend. Enthalpic barriers (ΔH(‡)) determined by the Eyring-Polanyi equation are in the range 14-19 kcal mol(-1) for all aryl azides studied. However, electron-donating 4-methoxyphenyl azide exhibits a large negative entropy of activation, ΔS(‡) = -21 cal mol(-1) K(-1), which is in sharp contrast to the near zero ΔS(‡) observed for phenyl azide and 4-(trifluoromethyl)phenyl azide. The Hammett linear free-energy relationship and the activation parameters support a change in the mechanism between electron-withdrawing and electron-donating aryl azides. Density functional theory predicts that the aryl azides coordinate via N(α) and extrude N(2) directly. For the electron-withdrawing substituents, N(2) extrusion is rate-determining, while for the electron-donating substituents, the rate-determining step becomes the initial attack of the azide. The barriers for these two steps are inverted in their order with respect to the Hammett σ values; thus, the Hammett plot appears with a break in its slope.

The green hemoproteins of bovine erythrocytes. II. Spectral, ligand-binding, and electrochemical properties.

PubMed

DeFilippi, L J; Hultquist, D E

1978-05-10

The two green hemoproteins isolated from bovine erythrocytes (form I and form II) have been characterized as to spectral, electrochemical, and chemical properties. The absorption spectra of the isolated hemoproteins are typical of high spin ferric states. Reduction of the hemoproteins yields high spin ferrohemoproteins. Complexation of the ferrohemoproteins with CO and the ferrihemoproteins with cyanide yields low spin complexes, demonstrating the presence of an exchangeable weak field ligand in both the ferrous and ferric states of the hemoproteins. The differences in position and intensity of the absorption peaks of the visible spectra allow the two forms to be distinguished from one another. The midpoint potential of forms I and II were found to be +0.075 and +0.019 V, respectively, at pH 6.4 and +0.038 and -0.005 V, respectively, at pH 7.0. This is consistent with the gaining of 1 proton/electron during the reduction. The Nernst plot reveals an unusual 0.5-electron transfer, whereas a quantitative titration demonstrates a 1-electron transfer. Form I binds cyanide more tightly than form II (KD of 84 and 252 micrometer, respectively). The observed spectral, electrochemical, and ligand-binding differences between forms I and II can be explained in terms of a greater electron-withdrawing ability of the side chains of the heme of form I relative to the heme of form II.

The electronic-cigarette: effects on desire to smoke, withdrawal symptoms and cognition.

PubMed

Dawkins, Lynne; Turner, John; Hasna, Surrayyah; Soar, Kirstie

2012-08-01

Electronic cigarettes (e-cigarettes) are battery operated devices that deliver nicotine via inhaled vapour. Few studies have evaluated acute effects on craving and mood, and none have explored effects on cognition. This study aimed to explore the effects of the White Super e-cigarette on desire to smoke, nicotine withdrawal symptoms, attention and working memory. Eighty-six smokers were randomly allocated to either: 18 mg nicotine e-cigarette (nicotine), 0mg e-cigarette (placebo), or just hold the e-cigarette (just hold) conditions. Participants rated their desire to smoke and withdrawal symptoms at baseline (T1), and five (T2) and twenty (T3) minutes after using the e-cigarette ad libitum for 5 min. A subset of participants completed the Letter Cancellation and Brown-Peterson Working Memory Tasks. After 20 min, compared with the just hold group, desire to smoke and some aspects of nicotine withdrawal were significantly reduced in the nicotine and placebo group; the nicotine e-cigarette was superior to placebo in males but not in females. The nicotine e-cigarette also improved working memory performance compared with placebo at the longer interference intervals. There was no effect of nicotine on Letter Cancellation performance. To conclude, the White Super e-cigarette alleviated desire to smoke and withdrawal symptoms 20 min after use although the nicotine content was more important for males. This study also demonstrated for the first time that the nicotine e-cigarette can enhance working memory performance. Further evaluation of the cognitive effects of the e-cigarette and its efficacy as a cessation tool is merited. Copyright © 2012 Elsevier Ltd. All rights reserved.

Electron Transport and Nonlinear Optical Properties of Substituted Aryldimesityl Boranes: A DFT Study

PubMed Central

Pandith, Altaf Hussain; Islam, Nasarul

2014-01-01

A comprehensive theoretical study was carried out on a series of aryldimesityl borane (DMB) derivatives using Density Functional theory. Optimized geometries and electronic parameters like electron affinity, reorganization energy, frontiers molecular contours, polarizability and hyperpolarizability have been calculated by employing B3PW91/6-311++G (d, p) level of theory. Our results show that the Hammett function and geometrical parameters correlates well with the reorganization energies and hyperpolarizability for the series of DMB derivatives studied in this work. The orbital energy study reveals that the electron releasing substituents increase the LUMO energies and electron withdrawing substituents decrease the LUMO energies, reflecting the electron transport character of aryldimesityl borane derivatives. From frontier molecular orbitals diagram it is evident that mesityl rings act as the donor, while the phenylene and Boron atom appear as acceptors in these systems. The calculated hyperpolarizability of secondary amine derivative of DMB is 40 times higher than DMB (1). The electronic excitation contributions to the hyperpolarizability studied by using TDDFT calculation shows that hyperpolarizability correlates well with dipole moment in ground and excited state and excitation energy in terms of the two-level model. Thus the results of these calculations can be helpful in designing the DMB derivatives for efficient electron transport and nonlinear optical material by appropriate substitution with electron releasing or withdrawing substituents on phenyl ring of DMB system. PMID:25479382

Anxiety Diagnoses in Smokers Seeking Cessation Treatment: Relations with Tobacco Dependence, Withdrawal, Outcome, and Response to Treatment

PubMed Central

Piper, Megan E.; Cook, Jessica W.; Schlam, Tanya R.; Jorenby, Douglas E.; Baker, Timothy B.

2010-01-01

Aims To understand the relations amongst anxiety disorders and tobacco dependence, withdrawal symptoms, response to smoking cessation pharmacotherapy, and ability to quit smoking. Design Randomized placebo-controlled clinical trial. Participants received six 10-minute individual counseling sessions and either: placebo, bupropion SR, nicotine patch, nicotine lozenge, bupropion SR+nicotine lozenge, or nicotine patch+nicotine lozenge. Setting Two urban research sites. Participants Data were collected from 1504 daily smokers (>9 cigarettes per day) who were motivated to quit smoking and did not report current diagnoses of schizophrenia or psychosis or bupropion use. Measurements Participants completed baseline assessments, the Composite International Diagnostic Interview and ecological momentary assessments for two weeks. Findings A structured clinical interview identified participants who ever met criteria for a panic attack (n=455), social anxiety (n=199), or generalized anxiety disorder (n=99), and those who qualified for no anxiety diagnosis (n=891). Smokers with anxiety disorders reported higher levels of nicotine dependence and pre-quit withdrawal symptoms. Those ever meeting criteria for panic attacks or social anxiety disorder showed greater quit-day negative affect. Smokers ever meeting criteria for anxiety disorders were less likely to be abstinent at 8-weeks and 6-months postquit and showed no benefit from single-agent or combination-agent pharmacotherapies. Conclusions Anxiety diagnoses were common amongst treatment-seeking smokers and were related to increased motivation to smoke, elevated withdrawal, lack of response to pharmacotherapy, and impaired ability to quit smoking. These findings could guide treatment assignment algorithms and treatment development for smokers with anxiety diagnoses. PMID:20973856

Attitudes and Approaches for Withdrawing Drugs for Children with Clinically Inactive Nonsystemic JIA: A Survey of the Childhood Arthritis and Rheumatology Research Alliance.

PubMed

Horton, Daniel B; Onel, Karen B; Beukelman, Timothy; Ringold, Sarah

2017-03-01

To assess the attitudes and strategies of pediatric rheumatology clinicians toward withdrawing medications for children with clinically inactive juvenile idiopathic arthritis (JIA). Members of the Childhood Arthritis and Rheumatology Research Alliance (CARRA) completed an anonymous electronic survey on decision making and approaches for withdrawing medications for inactive nonsystemic JIA. Data were analyzed using descriptive statistics. Of 388 clinicians in CARRA, 124 completed surveys (32%), predominantly attending pediatric rheumatologists. The most highly ranked factors in decision making for withdrawing medications were the duration of clinical inactivity, drug toxicity, duration of prior activity, patient/family preferences, joint damage, and JIA category. Diagnoses of rheumatoid factor-positive polyarthritis and persistent oligoarthritis made respondents less likely and more likely, respectively, to withdraw JIA medications. Three-quarters of respondents waited for 6-12 months of inactive disease before stopping methotrexate (MTX) or biologics, but preferences varied. There was also considerable variability in the strategies used to reduce, taper, or stop medications for clinically inactive JIA; most commonly, clinicians reported slow medication tapers lasting at least 2 months. For children receiving combination MTX-biologic therapy, 63% of respondents preferred stopping MTX first. Most clinicians reported using imaging only seldom or sometimes to guide decision making, but most were also reluctant to withdraw medications in the presence of asymptomatic imaging abnormalities suggestive of subclinical inflammation. Considerable variability exists among pediatric rheumatology clinicians regarding when and how to withdraw medications for children with clinically inactive JIA. More research is needed to identify the most effective approaches to withdraw medications and predictors of outcomes.

Computationally Designed Oligomers for High Contrast Black Electrochromic Polymers

DTIC Science & Technology

2017-05-05

SUBJECT TERMS electrochromics, DFf, TDDFT, organic electronics , oligomer, organic polymers 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF 18. NUMBER... electron -withdrawing behaviors. Another finding was that the same dication was produced regardless of the color or peak morphology of the neutral 5...radical cation states present in the chromophore upon oxidation. The two-ring electron rich dioxythiophene portions of the chromophore (EAc) and/or the

Combining the audit questionnaire and biochemical markers to assess alcohol use and risk of alcohol withdrawal in medical inpatients.

PubMed

Dolman, Jonathan M; Hawkes, Neil D

2005-01-01

Alcohol consumption is often under-reported in patients admitted to general hospitals with acute illness. For alcohol-dependent individuals hospital admission results in an enforced period of abstinence with potential alcohol withdrawal symptoms, and possible life threatening complications. Early detection of alcohol use is therefore beneficial to patients and health services. The purpose of this study was to investigate the performance of the alcohol use disorders identification test (AUDIT) questionnaire in the acute medical setting, and the effect of combining routine biological markers-glutamyltransferase, alanine aminotransferase, aspartate aminotransferase, and mean corpuscular volume (MCV) on its performance in the early identification of in-patients with alcohol use disorders and at risk of developing symptoms of alcohol withdrawal. Prospective study in consecutive patients admitted to an acute medical admissions ward. All patients were screened using the AUDIT questionnaire and routine blood tests. Patients were then monitored for symptoms of withdrawal using clinical institute withdrawal assessment for alcohol (CIWA-Ar). Of the 874 patients screened using the AUDIT, 98 (11%) screened positive of whom 17 (2% of the 874) experienced clinically significant alcohol withdrawal symptoms, when using serial CIWA-Ar. The AUDIT and serial CIWA-Ar detected all patients who went on to manifest acute withdrawal symptoms. There was no loss of sensitivity at an AUDIT cut-off of 13 or more compared with the lower cut-off of 8 or more. A positive predictive value of 17.3% for an AUDIT score of 8 or more in the detection of withdrawal, increased to 47.1% when found in combination with at least two abnormal biological markers whilst maintaining a sensitivity of 94.1% and specificity of 97.9%. These findings confirm that AUDIT is a useful alcohol screen in general medical settings and that its ability to correctly predict which patients will experience alcohol withdrawal is increased when used in combination with biological markers.

48 CFR 15.208 - Submission, modification, revision, and withdrawal of proposals.

Code of Federal Regulations, 2010 CFR

2010-10-01

... solicitation. Offerors may use any transmission method authorized by the solicitation (i.e., regular mail, electronic commerce, or facsimile). If no time is specified in the solicitation, the time for receipt is 4:30... not unduly delay the acquisition; and— (i) If it was transmitted through an electronic commerce method...

Comparison of tizanidine and morphine with regard to tolerance-developing ability to antinociceptive action.

PubMed

Nabeshima, T; Yamada, S; Sugimoto, A; Matsuno, K; Kameyama, T

1986-10-01

The antinociceptive, tolerance-developing and anti-withdrawal activities of tizanidine [5-chloro-4-(2-imidazolin-2-yl-amino)-2,1,3-benzo-thiadiazole] were investigated by comparing its effects with those of morphine and clonidine in tail-flick-, hot plate-, acetic acid-induced writhing-, and naloxone-precipitated withdrawal jumping-tests. The antinociceptive action of tizanidine was not altered by naloxone, while that of morphine was antagonized. Tolerance to the tizanidine-induced antinociceptive action and to motor incoordination was developed by successive administration of tizanidine. In the tizanidine-tolerant mice, the antinociceptive action of morphine was significantly decreased, but not sleeping time induced by pentobarbital. The action of tizanidine was not modified in the morphine-tolerant mice. Tizanidine failed to induce morphine-withdrawal jumping and to inhibit naloxone-precipitated withdrawal jumping in the morphine-dependent mice. Cross tolerance to the antinociceptive action induced by tizanidine and clonidine was developed. These results suggest that alpha 2-adrenoreceptors may be involved in the action mechanism of tizanidine, but not opioid receptors. Functional tolerance to tizanidine action may be developed by successive administration of tizanidine.

Acamprosate attenuates the handling induced convulsions during alcohol withdrawal in Swiss Webster mice

PubMed Central

Farook, Justin M.; Krazem, Ali; Littleton, John M.; Barron, Susan

2008-01-01

In the present study, we examined the effects of acamprosate for its ability to reduce handling induced convulsions (HICs) during alcohol withdrawal. Diazepam was used as a positive control. Swiss Webster male mice received three daily IP injections of alcohol (2.5 g/kg) or alcohol (2.5 g/kg) + methylpyrazole (4-MP) (9 mg/kg). (4-MP, being an alcohol dehydrogenase inhibitor slows down the breakdown of alcohol. 4-MP in combination with alcohol exhibits a dramatic increase in blood alcohol level compared to alcohol alone). Ten hours following the last alcohol injection, the mice were picked up by the tail and examined for their seizure susceptibility (HICs). Diazepam, a benzodiazepine known to reduce seizures during alcohol withdrawal, significantly reduced these HICs at doses of 0.25, 0.5 and 1mg/kg (p’s < 0.001). Acamprosate, an anti-relapse compound used clinically in newly abstinent alcoholics, also reduced these HICs at doses of 100, 200 and 300mg/kg (p’s < 0.05). This study supports the use of acamprosate during periods of alcohol withdrawal as well as during abstinence. PMID:18577392

78 FR 57456 - Submission for OMB Review; Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-18

... collection. Title: Information Regarding Request for Refund of Social Security Tax Erroneously Withheld on..., and, if applicable, consent to an electronic funds withdrawal. Affected Public: Private Sector...

Shy, but funny? Examining peer-valued characteristics as moderators of the associations between anxious-withdrawal and peer outcomes during early adolescence.

PubMed

Markovic, Andrea; Bowker, Julie C

2015-04-01

Research has revealed significant heterogeneity in the group-level peer outcomes associated with anxious-withdrawal, but little is known about possible sources of this heterogeneity during early adolescence. This study of 271 young adolescents (49 % female; M age = 11.54 years) examined whether the concurrent and short-term longitudinal (3 month period) associations between peer-nominated anxious-withdrawn behaviors and three group-level peer outcomes (overt victimization, peer acceptance, popularity) varied as a function of peer-valued characteristics (humor, prosocial behavior, physical attractiveness, athletic ability) and gender, after accounting for the effects of involvement in mutual friendships. Regression analyses revealed that the associations between anxious-withdrawal and peer outcomes were moderated by peer-valued characteristics and, in many cases, gender. For example, anxious-withdrawal was related positively to overt victimization for all adolescents who were high in prosocial behavior. But, anxious-withdrawal was related negatively to popularity for adolescent boys who were high in prosocial behavior and adolescent girls who were low in prosocial behavior. Anxious-withdrawal also predicted increases in acceptance for adolescent girls who were high in humor, but decreases in acceptance for adolescent boys who were high in humor. Several additional moderator effects were found for boys only. The findings highlight the importance of considering the unique constellation of characteristics displayed by anxious-withdrawn young adolescents in studies on peer experiences at the group-level of social complexity.

Distinct effects of protracted withdrawal on affect, craving, selective attention and executive functions among alcohol-dependent patients.

PubMed

Cordovil De Sousa Uva, Mariana; Luminet, Olivier; Cortesi, Marie; Constant, Eric; Derely, Marc; De Timary, Philippe

2010-01-01

The present study examined the effects of protracted alcohol withdrawal on affectivity, craving, selective attention and executive functions (EFs) in alcohol-dependent patients. Selective attention (The D2 Cancellation Test), flexibility (Trail Making Test), inhibition (Stroop Task), decision making (Iowa Gambling Task), craving (Obsessive-Compulsive Drinking Scale) and state affectivity (Positive and Negative Affectivity Schedule) were assessed in alcohol-dependent patients (DSM-IV, n = 35) matched to non-alcohol-dependent participants (n = 22) at the onset (T1: day 1 or 2) and at the end (T2: days 14-18) of protracted withdrawal during rehab. Alcohol-dependent patients' abilities to focus their attention on relevant information, to switch from one pattern to another, to inhibit irrelevant information and to make advantageous choices were lower than those of control participants during both times of a withdrawal cure. No effect of time emerged from analyses for selective attention and EF deficits. Conversely, significant differences between T1 and T2 were observed for craving and affect scores indicating a weakening of alcohol craving and negative affect as well as an improvement of positive affect among patients from onset to the end of cure. Control functions of the Supervisory Attentional System (Norman and Shallice, 1986) were impaired and did not improve during a 3-week withdrawal cure, whereas alcohol craving and negative state affectivity significantly improved in parallel during this period. Implications for understanding the clinical processes of withdrawal are discussed.

Density Functional Study on A-Units Based on Thieno[3,4- c]pyrrole-4,6-dione for Organic Solar Cells

NASA Astrophysics Data System (ADS)

Tang, Xiaoqin; Shen, Wei; Fu, Zhiyong; Liu, Xiaorui; Li, Ming

2017-08-01

The use of polymer donor materials has allowed great progress in organic solar cells. To search for potential donor materials, we have designed a series of donor-acceptor (D-A)-type alternating polymers composed of dithieno[3,2- b:2',3'- d]pyrrole (DTP) electron-rich units and thieno[3,4- c]pyrrole-4,6-dione (TPD) electron-deficient units. Their electronic and optical properties have been investigated using density functional theory and Marcus theory. The calculation results demonstrate that introduction of cyclic compounds (furyl, thienyl, and phenyl) into electron-deficient units of the molecules can result in lower highest occupied molecular orbital (HOMO) levels and reorganization energies compared with the experimental molecule ( X 0 ). To investigate the effects of electron-withdrawing units, three electron-withdrawing substituents (-OCH3, -F, and -CN) were introduced into the thienyl. The results indicated that the polymer X 2-3 will show the best performance among the designed polymers, offering low-lying HOMO energy level (-5.47 eV), narrow energy gap (1.97 eV), and high hole mobility (7.45 × 10-2 cm2 V-1 s-1). This work may provide a guideline for the design of efficient D-A polymers for organic solar cells with enhanced performance.

Nephrologists' perceptions regarding dialysis withdrawal and palliative care in Europe: lessons from a European Renal Best Practice survey

PubMed Central

van Biesen, Wim; van de Luijtgaarden, Moniek W.M.; Brown, Edwina A.; Michel, Jean-Pierre; van Munster, Barbara C.; Jager, Kitty J.; van der Veer, Sabine N.

2015-01-01

Background There is a variation in dialysis withdrawal rates, but reasons for this variation across European countries are largely unknown. We therefore surveyed nephrologists' perceptions of factors concerning dialysis withdrawal and palliative care and explored relationships between these perceptions and reports of whether withdrawal actually occurred in practice. Methods We developed a 33-item electronic survey, disseminated via an email blast to all European Renal Association–European Dialysis and Transplant Association (ERA-EDTA) members. In our data analyses, we distinguished those respondents who reported occurrence from those reporting no dialysis withdrawal in their unit. With multilevel logistic regression, we investigated the association between respondents' characteristics and perceptions and whether they reported occurrence of dialysis withdrawal or not. Results Five hundred and twenty-eight nephrologists from 45 countries completed the questionnaire; 42% reported occurrence of withdrawal in their unit in the past year, and 56% perceived that stopping life-prolonging treatment in terminally ill patients was allowed. Few respondents reported presence in their unit of protocols on withdrawal decision making (7%) or palliative care (10%) or the common involvement of a geriatrician in withdrawal decisions (10%). The majority stated that palliative care had not been part of their core curriculum (74%) and that they had not recently attended continuous medical education sessions on this topic (73%). Respondents from Eastern and Southern Europe had a 42 and 40% lower probability, respectively, of reporting withdrawal compared with those from North European countries. Working in a public centre [odds ratio (OR), 2.41; 95% confidence interval (CI), 1.36–4.25] and respondents' perception that stopping life-prolonging treatment in terminally ill patients was allowed (OR, 1.96; 95% CI, 1.23–3.12), that withdrawal decisions were commonly shared between doctor and patient (OR, 1.97; 95% CI, 1.26–3.08) and that palliative care was reimbursed (OR, 1.81; 95% CI, 1.16–2.83) increased the odds of reporting occurrence of withdrawal. Conclusion Reports of dialysis withdrawal occurrence varied between European countries. Occurrence reports were more likely if respondents worked in a public centre, if stopping life-prolonging treatments was perceived as allowed, if withdrawal decisions were considered shared between doctors and patients and if reimbursement of palliative care was believed to be in place. There is room for improvement regarding protocols on withdrawal and palliative care processes and regarding nephrologists' training and education on end-of-life care. PMID:26268713

Treatment for amphetamine withdrawal.

PubMed

Srisurapanont, M; Jarusuraisin, N; Kittirattanapaiboon, P

2001-01-01

Amphetamine withdrawal has been less studied although it is a common problem with a prevalent rate of 87% among amphetamine users. Its symptoms, in particular intense craving, may be a critical factor leading to relapse of amphetamine use. In clinical practice, treatment for cocaine withdrawal has been recommended for the management of amphetamine withdrawal although the pharmacodynamic and pharmacokinetic properties of these two substances are not the same. To search and determine risks, benefits, and costs of a variety of treatments for the management of amphetamine withdrawal. Electronic searches of MEDLINE (1966 - December 2000), EMBASE (1980 - February 2001), CINAHL (1982 - January 2001) and Cochrane Controlled Trials Register (Cochrane Library 2000 issue 4) were undertaken. References to the articles obtained by any means were searched. All relevant randomised controlled trials (RCTs) and controlled clinical trials (CCTs) were included. Participants were people with amphetamine withdrawal, diagnosed by any set of criteria. Any kinds of biological and psychological treatments both alone and combined were examined. A variety of outcomes, for example, number of treatment responders, score changes, were considered. Two reviewers evaluated and extracted the data independently. The dichotomous data were extracted on an intention-to-treat basis in which the dropouts were assigned as participants with the worst outcomes. The Relative Risk (RR) with the 95% confidence interval (95% CI) was used to assess the dichotomous data. The Weighted Mean Difference (WMD) with 95% CI was used to assessed the continuous data. The results of two studies have shown some benefits of amineptine in the treatment of amphetamine withdrawal. Those benefits can be seen in the respects of discontinuation rate and global state, as measured by Clinical Global Impression Scale. However, no direct benefit of amineptine on amphetamine withdrawal symptoms or craving was shown. The evidence about the treatment for amphetamine withdrawal is very limited. Amineptine has limited benefits on some amphetamine withdrawal symptoms. Due to a number of reports of amineptine abuse, it has been withdrawn from the market for a few years. At present, no available treatment has been demonstrated to be effective in the treatment of amphetamine withdrawal. The medications that should be considered for further treatment studies may be those with the propensities to increase dopamine, norepinephrine and/or serotonin activities of the brain. Naturalistic studies of amphetamine withdrawal symptoms and course are also crucial for the development of study designs appropriate for further treatment studies of amphetamine withdrawal.

Attitudes and approaches for withdrawing drugs for children with clinically inactive non-systemic JIA: a survey of the Childhood Arthritis and Rheumatology Research Alliance

PubMed Central

Horton, Daniel B.; Onel, Karen B.; Beukelman, Timothy; Ringold, Sarah

2016-01-01

Objective To assess the attitudes and strategies of pediatric rheumatology clinicians towards withdrawing medications for children with clinically inactive juvenile idiopathic arthritis (JIA). Methods Members of the Childhood Arthritis and Rheumatology Research Alliance (CARRA) completed an anonymous electronic survey on decision-making and approaches for withdrawing medications for inactive non-systemic JIA. Data were analyzed using descriptive statistics. Results Of 388 clinicians in CARRA, 124 completed surveys (32%), predominantly attending pediatric rheumatologists. The most highly ranked factors in decision-making for withdrawing medications were duration of clinical inactivity, drug toxicity, duration of prior activity, patient/family preferences, joint damage, and JIA category. Diagnoses of RF-positive polyarthritis and persistent oligoarthritis made respondents less likely and more likely, respectively, to withdraw JIA medications. Three-quarters of respondents waited for 6–12 months of inactive disease before stopping methotrexate or biologics, but preferences varied. There was also considerable variability in the strategies used to reduce, taper, or stop medications for clinically inactive JIA; most commonly, clinicians reported slow medication tapers lasting at least 2 months. For children on combination methotrexate-biologic therapy, 63% of respondents preferred stopping methotrexate first. Most clinicians reported using imaging only seldom or sometimes to guide decision-making, but most were also reluctant to withdraw medications in the presence of asymptomatic imaging abnormalities suggestive of subclinical inflammation. Conclusion Considerable variability exists among pediatric rheumatology clinicians regarding when and how to withdraw medications for children with clinically inactive JIA. More research is needed to identify the most effective approaches to withdraw medications and predictors of outcomes. PMID:28148696

A case of methimazole-induced hypothyroidism in a patient with endemic goiter: effects of endogenous TSH hyperstimulation after discontinuation of the drug.

PubMed

Messina, M; Manieri, C; Spagnuolo, F; Sardi, E; Allegramente, L; Monaco, A; Ciccarelli, E

1989-04-01

Serum thyroid hormone and TSH concentrations were monitored in a patient with multinodular endemic goiter and severe methimazole (MMI) induced hypothyrodism up to 190 days after drug withdrawal. Serum concentrations of TT3, TT4 and TSH returned to normal values at the 6th., the 140th, and the 120th. day respectively. Within the first 20 days after MMI withdrawal the increase of serum T3 levels was correlated with the observed decrease of serum TSH concentrations. Successively T3 values decreased and T4 levels progressively increased. Six months after MMI withdrawal basal serum TSH concentration was normal while an exaggerated response to TRH was observed. We think that this peculiar hormone pattern is due to iodine depletion. In this case TSH hyperstimulation increases predominantly T3 secretion demonstrating the reduced thyroidal ability to produce T4 when hyperstimulated.

Synthesis, Properties, Calculations and Applications of Small Molecular Host Materials Containing Oxadiazole Units with Different Nitrogen and Oxygen Atom Orientations for Solution-Processable Blue Phosphorescent OLEDs

NASA Astrophysics Data System (ADS)

Ye, Hua; Wu, Hongyu; Chen, Liangyuan; Ma, Songhua; Zhou, Kaifeng; Yan, Guobing; Shen, Jiazhong; Chen, Dongcheng; Su, Shi-Jian

2018-03-01

A series of new small molecules based on symmetric electron-acceptor of 1,3,4-oxadiazole moiety or its asymmetric isomer of 1,2,4-oxadiazole unit were successfully synthesized and applied to solution-processable blue phosphorescent organic light-emitting diodes for the first time, and their thermal, photophysical, electrochemical properties and density functional theory calculations were studied thoroughly. Due to the high triplet energy levels ( E T, 2.82-2.85 eV), the energy from phosphorescent emitter of iridium(III) bis[(4,6-difluorophenyl)-pyridinate- N,C2']picolinate (FIrpic) transfer to the host molecules could be effectively suppressed and thus assuring the emission of devices was all from FIrpic. In comparison with the para-mode conjugation in substitution of five-membered 1,3,4-oxadiazole in 134OXD, the meta-linkages of 1,2,4-isomer appending with two phenyl rings cause the worse conjugation degree and the electron delocalization as well as the lower electron-withdrawing ability for the other 1,2,4-oxadiazole-based materials. Noting that the solution-processed device based on 134OXD containing 1,3,4-oxadiazole units without extra vacuum thermal-deposited hole/exciton-blocking layer and electron-transporting layer showed the highest maximum current efficiency (CEmax) of 8.75 cd/A due to the excellent charge transporting ability of 134OXD, which far surpassed the similar devices based on other host materials containing 1,2,4-oxadiazole units. Moreover, the device based on 134OXD presented small efficiency roll-off with current efficiency (CE) of 6.26 cd/A at high brightness up to 100 cd/m2. This work demonstrates different nitrogen and oxygen atom orientations of the oxadiazole-based host materials produce major impact on the optoelectronic characteristics of the solution-processable devices.

Simulating the effects of ground-water withdrawals on streamflow in a precipitation-runoff model

USGS Publications Warehouse

Zarriello, Philip J.; Barlow, P.M.; Duda, P.B.

2004-01-01

Precipitation-runoff models are used to assess the effects of water use and management alternatives on streamflow. Often, ground-water withdrawals are a major water-use component that affect streamflow, but the ability of surface-water models to simulate ground-water withdrawals is limited. As part of a Hydrologic Simulation Program-FORTRAN (HSPF) precipitation-runoff model developed to analyze the effect of ground-water and surface-water withdrawals on streamflow in the Ipswich River in northeastern Massachusetts, an analytical technique (STRMDEPL) was developed for calculating the effects of pumped wells on streamflow. STRMDEPL is a FORTRAN program based on two analytical solutions that solve equations for ground-water flow to a well completed in a semi-infinite, homogeneous, and isotropic aquifer in direct hydraulic connection to a fully penetrating stream. One analytical method calculates unimpeded flow at the stream-aquifer boundary and the other method calculates the resistance to flow caused by semipervious streambed and streambank material. The principle of superposition is used with these analytical equations to calculate time-varying streamflow depletions due to daily pumping. The HSPF model can readily incorporate streamflow depletions caused by a well or surface-water withdrawal, or by multiple wells or surface-water withdrawals, or both, as a combined time-varying outflow demand from affected channel reaches. These demands are stored as a time series in the Watershed Data Management (WDM) file. This time-series data is read into the model as an external source used to specify flow from the first outflow gate in the reach where these withdrawals are located. Although the STRMDEPL program can be run independently of the HSPF model, an extension was developed to run this program within GenScn, a scenario generator and graphical user interface developed for use with the HSPF model. This extension requires that actual pumping rates for each well be stored in a unique WDM dataset identified by an attribute that associates each well with the model reach from which water is withdrawn. Other attributes identify the type and characteristics of the data. The interface allows users to easily add new pumping wells, delete exiting pumping wells, or change properties of the simulated aquifer or well. Development of this application enhanced the ability of the HSPF model to simulate complex water-use conditions in the Ipswich River Basin. The STRMDEPL program and the GenScn extension provide a valuable tool for water managers to evaluate the effects of pumped wells on streamflow and to test alternative water-use scenarios. Copyright ASCE 2004.

Synthesis and Biological Screening of Pyrano[3,2-c]quinoline Analogues as Anti-inflammatory and Anticancer Agents.

PubMed

Upadhyay, Kuldip D; Dodia, Narsinh M; Khunt, Rupesh C; Chaniara, Ravi S; Shah, Anamik K

2018-03-08

A series of pyrano[3,2- c ]quinoline based structural analogues was synthesized using one-pot multicomponent condensation between 2,4-dihydroxy-1-methylquinoline, malononitrile, and diverse un(substituted) aromatic aldehydes. The synthesized compounds were evaluated for their anti-inflammatory and cytotoxicity activity. Initially, all the compounds were evaluated for the percent inhibition of cytokine release, and cytotoxicity activity and 50% inhibitory concentrations (IC 50 ) were also determined. Based on the primary results, it was further studied for their ability to inhibit TNF-α production in the human peripheral blood mononuclear cells (hPBMC) assay. The screening results revealed that compound 4c , 4f , 4i , and 4j were found most active candidates of the series against both anti-inflammatory and anticancer activity. The structure-activity relationship is discussed and suggested that 3-substitution on the aryl ring at C4 position of the pyrano[3,2- c ]quinolone structural motif seems to be an important position for both TNF-α and IL-6 inhibition and anticancer activity as well. However, structural diversity with electron withdrawing, electron donating, sterically hindered, and heteroaryl substitution sincerely affected both the inflammation and anticancer activities.

Decision support during electronic prescription to stem antibiotic overuse for acute respiratory infections: a long-term, quasi-experimental study.

PubMed

Gifford, Jeneen; Vaeth, Elisabeth; Richards, Katherine; Siddiqui, Tariq; Gill, Christine; Wilson, Lucy; DeLisle, Sylvain

2017-07-31

Interventions to support decision-making can reduce inappropriate antibiotic use for acute respiratory infections (ARI), but they may not be sustainable. The objective of the study is to evaluate the long-term effectiveness of a clinical decision-support system (CDSS) interposed at the time of electronic (e-) prescriptions for selected antibiotics. This is a retrospective, observational intervention study, conducted within a large, statewide Veterans Affairs health system. Participants are outpatients with an initial visit for ARI. A CDSS was deployed upon e-prescription of selected antibiotics during the study period. From 01/2004 to 05/2006 (pre-withdrawal period), the CDSS targeted azithromycin and the fluoroquinolone gatifloxacin. From 05/2006 to 12/2011 (post-withdrawal period), the CDSS was retained for azithromycin but withdrawn for the fluoroquinolone. A manual record review was conducted to determine concordance of antibiotic prescription with ARI treatment guidelines. Of 1131 included ARI visits, 380 (33.6%) were guideline-concordant. For azithromycin, concordance did not change between the pre- and post-withdrawal periods, and adjusted odds of concordance was 8.8 for the full study period, compared to unrestricted antibiotics. For fluoroquinolones, guideline concordance decreased from 88.6% (39 of 44 visits) to 51.3% (59 of 115 visits), pre- vs. post-withdrawal periods (p < 0.005). The adjusted odds of concordance compared to "All Other Antibiotics" visits decreased from 24.4 (95% CI 9.0-66.3) pre-withdrawal to 5.5 (95% CI 3.5-8.8) post-withdrawal (p = .008). Concordance did not change between those same time periods for antibiotics that were never subjected to the intervention ("All Other Antibiotics"). A CDSS interposed at the time of e-prescription of selected antibiotics can shift their use toward ARI treatment guidelines, and this effect can be maintained over the long term as long as the CDSS remains in place. Removal of the CDSS after 3.5 years of implementation resulted in a rise in guideline-discordant antibiotic use.

Post-Marketing Regulation of Medicines Withdrawn from the Market Because of Drug-Attributed Deaths: An Analysis of Justification.

PubMed

Onakpoya, Igho J; Heneghan, Carl J; Aronson, Jeffrey K

2017-05-01

Several medicinal products have been withdrawn from the market because of drug-attributed deaths. However, there has been no investigation of whether such withdrawals were justified, and the extent to which confirmatory studies are used to investigate drug-adverse event relationships when deaths are reported is uncertain. We documented medicinal products withdrawn from the market because of drug-attributed deaths, identified confirmatory studies investigating the drug-adverse event relationships, examined whether withdrawals of medicinal products because of drug-attributed deaths after marketing were justified based on a mechanistic analysis, and examined the trends over time. We searched electronic and non-electronic sources to identify medicinal products that were withdrawn because of drug-attributed deaths. We used a previously published algorithm to examine whether the withdrawals of products were justified. We then searched PubMed and Google Scholar to identify studies investigating the drug-adverse event relationships, used the Oxford Centre for Evidence-Based Medicine criteria to document the levels of evidence, and assessed whether the evidence of an association was confirmed. We included 83 medicinal products. The reasons for withdrawal appeared to have been justified in 80 cases (96%). The median interval between the first reported adverse reaction that was related to the cause of death and the first reported death was 1 year (interquartile range = 1-3); products were withdrawn sooner when the interval between the first reported relevant adverse reaction and the first death was shorter. Confirmatory studies were conducted in 57 instances (69%), and there was evidence of an association in 52 cases (63%). Four products (5%) were re-introduced after initial withdrawal. Regulatory authorities have been justified in making withdrawal decisions when deaths have been attributed to medicinal products, using the precautionary principle when alternative decisions could have been made. Medicinal products are likely to be quickly withdrawn from the market when there is a short interval to the first reported deaths. The use of an algorithm such as we have used in this study could help to expedite the process of decision making.

12 CFR 330.1 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... means a form of business in which one person owns all the assets of the business, in contrast to a..., payment orders of withdrawal, telephone or other electronic media transfers, or other similar items for...

12 CFR Part 745 - SHARE INSURANCE AND APPENDIX

Code of Federal Regulations, 2013 CFR

2013-01-01

..., payment orders of withdrawal, telephone or other electronic media transfers, or other similar items for... in good faith and in the regular course of business. (3) The account records of an insured credit...

12 CFR Part 745 - SHARE INSURANCE AND APPENDIX

Code of Federal Regulations, 2012 CFR

2012-01-01

..., payment orders of withdrawal, telephone or other electronic media transfers, or other similar items for... in good faith and in the regular course of business. (3) The account records of an insured credit...

16 CFR 1303.5 - Findings.

Code of Federal Regulations, 2012 CFR

2012-01-01

... designed to eliminate or reduce is lead poisoning in children. The adverse effects of this poisoning in children can cause a range of disorders such as hyperactivity, slowed learning ability, withdrawal... functional disorders which are often included under the heading of minimal brain dysfunction. Studies suggest...

16 CFR 1303.5 - Findings.

Code of Federal Regulations, 2010 CFR

2010-01-01

... designed to eliminate or reduce is lead poisoning in children. The adverse effects of this poisoning in children can cause a range of disorders such as hyperactivity, slowed learning ability, withdrawal... functional disorders which are often included under the heading of minimal brain dysfunction. Studies suggest...

16 CFR 1303.5 - Findings.

Code of Federal Regulations, 2011 CFR

2011-01-01

... designed to eliminate or reduce is lead poisoning in children. The adverse effects of this poisoning in children can cause a range of disorders such as hyperactivity, slowed learning ability, withdrawal... functional disorders which are often included under the heading of minimal brain dysfunction. Studies suggest...

16 CFR 1303.5 - Findings.

Code of Federal Regulations, 2014 CFR

2014-01-01

... designed to eliminate or reduce is lead poisoning in children. The adverse effects of this poisoning in children can cause a range of disorders such as hyperactivity, slowed learning ability, withdrawal... functional disorders which are often included under the heading of minimal brain dysfunction. Studies suggest...

Postoperative chest tube management: measuring air leak using an electronic device decreases variability in the clinical practice.

PubMed

Varela, Gonzalo; Jiménez, Marcelo F; Novoa, Nuria Maria; Aranda, José Luis

2009-01-01

Since there are no data in the literature regarding variability in the management of postoperative pleural drainages, we have designed a prospective randomized study aimed at measuring inter-observer variability in deciding when to withdraw chest tubes after lung resection and to evaluate if the use of an electronic device to measure postoperative air leak decreases clinical practice variations. Sixty-one patients undergoing pulmonary resection were randomly assigned to one of the following groups: digital group (electronic measure of pleural air leak using Millicore AB DigiVent chest drainage system) or traditional group (standard water seal pleural chamber). Chest tube withdrawal criteria were established in advance. During morning rounds, two thoracic surgeons with comparable clinical experience and blinded to the decision of their counterpart, evaluated chest tube withdrawal criteria and noted whether the tube should be withdrawn or not. Inter-observer variability kappa index and global, positive, and negative agreement rates were calculated on 2 x 2 tables. Each observation episode was considered in the calculation. Fifty-four observations were recorded in the traditional group. Kappa coefficient was 0.37 (overall agreement rate: 0.58; positive agreement rate: 0.72; and negative agreement rate: 0.64). In the digital group, 67 observations were recorded. Kappa coefficient was 0.88 (overall agreement rate: 0.94; positive agreement rate 0.94; and negative agreement rate 0.94). We have demonstrated a high rate of disagreement related to the indication to remove chest tubes after lung resection and the improvement of the agreement rate with the use of an electronic device to measure postoperative air leak and pleural pressures.

Using Hematology Data from Malaria Vaccine Research Trials in Humans and Rhesus Macaques (Macaca mulatta) To Guide Volume Limits for Blood Withdrawal.

PubMed

Hegge, Sara R; Hickey, Bradley W; Mcgrath, Shannon M; Stewart, V Ann

2016-12-01

Guidelines on safe volume limits for blood collection from research participants in both humans and laboratory animals vary widely between institutions. The main adverse event that may be encountered in large blood volume withdrawal is iron-deficiency anemia. Monitoring various parameters in a standard blood panel may help to prevent this outcome. To this end, we analyzed the Hgb and MCV values from 43 humans and 46 macaques in malaria vaccine research trials. Although the percentage of blood volume removed was greater for macaques than humans, macaques demonstrated an overall increase of MCV over time, indicating the ability to respond appropriately to frequent volume withdrawals. In contrast, humans showed a consistent declining trend in MCV. These declines in human MCV and Hgb were significant from the beginning to end of the study despite withdrawals that were smaller than recommended volume limits. Limiting the volume withdrawn to no more than 12.5% seemed to be sufficient for macaques, and at 14% or more individual animals tended to fail to respond appropriately to large-volume blood loss, as demonstrated by a decrease in MCV. The overall positive erythropoietic response seen in macaques was likely due to the controlled, iron-fortified diet they received. The lack of erythropoietic response in the human subjects may warrant iron supplementation or reconsideration of current blood volume withdrawal guidelines.

Evaluation and comparison of methods to estimate irrigation withdrawal for the National Water Census Focus Area Study of the Apalachicola-Chattahoochee-Flint River Basin in southwestern Georgia

USGS Publications Warehouse

Painter, Jaime A.; Torak, Lynn J.; Jones, John W.

2015-09-30

Methods to estimate irrigation withdrawal using nationally available datasets and techniques that are transferable to other agricultural regions were evaluated by the U.S. Geological Survey as part of the Apalachicola-Chattahoochee-Flint (ACF) River Basin focus area study of the National Water Census (ACF–FAS). These methods investigated the spatial, temporal, and quantitative distributions of water withdrawal for irrigation in the southwestern Georgia region of the ACF–FAS, filling a vital need to inform science-based decisions regarding resource management and conservation. The crop– demand method assumed that only enough water is pumped onto a crop to satisfy the deficit between evapotranspiration and precipitation. A second method applied a geostatistical regimen of variography and conditional simulation to monthly metered irrigation withdrawal to estimate irrigation withdrawal where data do not exist. A third method analyzed Landsat satellite imagery using an automated approach to generate monthly estimates of irrigated lands. These methods were evaluated independently and compared collectively with measured water withdrawal information available in the Georgia part of the ACF–FAS, principally in the Chattahoochee-Flint River Basin. An assessment of each method’s contribution to the National Water Census program was also made to identify transfer value of the methods to the national program and other water census studies. None of the three methods evaluated represent a turnkey process to estimate irrigation withdrawal on any spatial (local or regional) or temporal (monthly or annual) extent. Each method requires additional information on agricultural practices during the growing season to complete the withdrawal estimation process. Spatial and temporal limitations inherent in identifying irrigated acres during the growing season, and in designing spatially and temporally representative monitor (meter) networks, can belie the ability of the methods to produce accurate irrigation-withdrawal estimates that can be used to produce dependable and consistent assessments of water availability and use for the National Water Census. Emerging satellite-data products and techniques for data analysis can generate high spatial-resolution estimates of irrigated-acres distributions with near-term temporal frequencies compatible with the needs of the ACF–FAS and the National Water Census.

The unexpected roles of σ and π orbitals in electron donor and acceptor group effects on the 13C NMR chemical shifts in substituted benzenes† †Electronic supplementary information (ESI) available: Experimental 13C NMR chemical shifts, individual components of the 13C NMR shielding tensor, lists and graphics of NLMO contributions, and tables of NLMO properties. See DOI: 10.1039/c7sc02163a Click here for additional data file.

PubMed Central

Viesser, Renan V.

2017-01-01

Effects of electron-donating (R = NH2) and electron-withdrawing (R = NO2) groups on 13C NMR chemical shifts in R-substituted benzene are investigated by molecular orbital analyses. The 13C shift substituent effect in ortho, meta, and para position is determined by the σ bonding orbitals in the aryl ring. The π orbitals do not explain the substituent effects in the NMR spectrum as conventionally suggested in textbooks. The familiar electron donating and withdrawing effects on the π system by NH2 and NO2 substituents induce changes in the σ orbital framework, and the 13C chemical shifts follow the trends induced in the σ orbitals. There is an implicit dependence of the σ orbital NMR shift contributions on the π framework, via unoccupied π* orbitals, due to the fact that the nuclear shielding is a response property. PMID:28989684

19 CFR 122.78 - Entry or withdrawal for exportation or for transportation and exportation.

Code of Federal Regulations, 2010 CFR

2010-04-01

..., DEPARTMENT OF HOMELAND SECURITY; DEPARTMENT OF THE TREASURY AIR COMMERCE REGULATIONS Documents Required for Clearance and Permission To Depart; Electronic Manifest Requirements for Passengers, Crew Members, and Non...

Sex Differences in Ethanol's Anxiolytic Effect and Chronic Ethanol Withdrawal Severity in Mice with a Null Mutation of the 5α-Reductase Type 1 Gene.

PubMed

Tanchuck-Nipper, Michelle A; Ford, Matthew M; Hertzberg, Anna; Beadles-Bohling, Amy; Cozzoli, Debra K; Finn, Deborah A

2015-05-01

Manipulation of endogenous levels of the GABAergic neurosteroid allopregnanolone alters sensitivity to some effects of ethanol. Chronic ethanol withdrawal decreases activity and expression of 5α-reductase-1, an important enzyme in allopregnanolone biosynthesis encoded by the 5α-reductase-1 gene (Srd5a1). The present studies examined the impact of Srd5a1 deletion in male and female mice on several acute effects of ethanol and on chronic ethanol withdrawal severity. Genotype and sex did not differentially alter ethanol-induced hypothermia, ataxia, hypnosis, or metabolism, but ethanol withdrawal was significantly lower in female versus male mice. On the elevated plus maze, deletion of the Srd5a1 gene significantly decreased ethanol's effect on total entries versus wildtype (WT) mice and significantly decreased ethanol's anxiolytic effect in female knockout (KO) versus WT mice. The limited sex differences in the ability of Srd5a1 genotype to modulate select ethanol effects may reflect an interaction between developmental compensations to deletion of the Srd5a1 gene with sex hormones and levels of endogenous neurosteroids.

Sex Differences in Ethanol’s Anxiolytic Effect and Chronic Ethanol Withdrawal Severity in Mice With a Null Mutation of the 5α-Reductase Type 1 Gene

PubMed Central

Tanchuck-Nipper, Michelle A.; Ford, Matthew M.; Hertzberg, Anna; Beadles-Bohling, Amy; Cozzoli, Debra K.; Finn, Deborah A.

2015-01-01

Manipulation of endogenous levels of the GABAergic neurosteroid allopregnanolone alters sensitivity to some effects of ethanol. Chronic ethanol withdrawal decreases activity and expression of 5α-reductase-1, an important enzyme in allopregnanolone biosynthesis encoded by the 5α-reductase-1 gene (Srd5a1). The present studies examined the impact of Srd5a1 deletion in male and female mice on several acute effects of ethanol and on chronic ethanol withdrawal severity. Genotype and sex did not differentially alter ethanol-induced hypothermia, ataxia, hypnosis, or metabolism, but ethanol withdrawal was significantly lower in female versus male mice. On the elevated plus maze, deletion of the Srd5a1 gene significantly decreased ethanol’s effect on total entries versus wildtype (WT) mice and significantly decreased ethanol’s anxiolytic effect in female knockout (KO) versus WT mice. The limited sex differences in the ability of Srd5a1 genotype to modulate select ethanol effects may reflect an interaction between developmental compensations to deletion of the Srd5a1 gene with sex hormones and levels of endogenous neurosteroids. PMID:25355320

Oxidative versus Non-oxidative Decarboxylation of Amino Acids: Conditions for the Preferential Formation of Either Strecker Aldehydes or Amines in Amino Acid/Lipid-Derived Reactive Carbonyl Model Systems.

PubMed

Zamora, Rosario; León, M Mercedes; Hidalgo, Francisco J

2015-09-16

Comparative formation of both 2-phenylethylamine and phenylacetaldehyde as a consequence of phenylalanine degradation by carbonyl compounds was studied in an attempt to understand if the amine/aldehyde ratio can be changed as a function of reaction conditions. The assayed carbonyl compounds were selected because of the presence in the chain of both electron-donating and electron-withdrawing groups and included alkenals, alkadienals, epoxyalkenals, oxoalkenals, and hydroxyalkenals as well as lipid hydroperoxides. The obtained results showed that the 2-phenylethylamine/phenylacetaldehyde ratio depended upon both the carbonyls and the reaction conditions. Thus, it can be increased using electron-donating groups in the chain of the carbonyl compound, small amounts of carbonyl compound, low oxygen content, increasing the pH, or increasing the temperature at pH 6. Opposed conditions (use of electron-withdrawing groups in the chain of the carbonyl compound, large amounts of carbonyl compound, high oxygen contents, low pH values, and increasing temperatures at low pH values) would decrease the 2-phenylethylamine/phenylacetaldehyde ratio, and the formation of aldehydes over amines in amino acid degradations would be favored.

Psychiatric aspects of acute withdrawal from gamma-hydroxybutyrate (GHB) and its analogue gamma-butyrolactone (GBL): implications for psychiatry services in the general hospital.

PubMed

Choudhuri, Debajeet; Cross, Sean; Dargan, Paul I; Wood, David M; Ranjith, Gopinath

2013-06-01

The objective of this study was to describe the psychiatric symptoms, management and outcomes in a consecutive series of patients being managed medically for symptoms of withdrawal from gamma-hydroxybutyrate (GHB) and its analogue gamma-butyrolactone (GBL) in a general hospital setting. A toxicology database was used to identify patients presenting with a history suggestive of withdrawal from GHB and analogues. Electronic and paper medical records were searched for demographic features, neuropsychiatric symptoms, psychiatric management while in hospital and overall outcome. There were 31 presentations with withdrawal from the drugs involving 20 patients. Of these 17 (54%) were referred to and seen by the liaison psychiatry team. Anxiety (61.3%) and agitation (48.4%) were the most common symptoms. Of the 17 cases seen by the liaison psychiatry team, 52.9% required close constant observation by a mental health nurse and 29.4% required to be detained in hospital under mental health legislation. The significant proportion of patients presenting with neuropsychiatric symptoms and requiring intensive input from the liaison psychiatry team during withdrawal from GHB and its analogues points to the importance of close liaison between medical and psychiatric teams in managing these patients in the general hospital.

Update to the Ground-Water Withdrawals Database for the Death Valley Regional Ground-Water Flow System, Nevada and California, 1913-2003

USGS Publications Warehouse

Moreo, Michael T.; Justet, Leigh

2008-01-01

Ground-water withdrawal estimates from 1913 through 2003 for the Death Valley regional ground-water flow system are compiled in an electronic database to support a regional, three-dimensional, transient ground-water flow model. This database updates a previously published database that compiled estimates of ground-water withdrawals for 1913-1998. The same methodology is used to construct each database. Primary differences between the 2 databases are an additional 5 years of ground-water withdrawal data, well locations in the updated database are restricted to Death Valley regional ground-water flow system model boundary, and application rates are from 0 to 1.5 feet per year lower than original estimates. The lower application rates result from revised estimates of crop consumptive use, which are based on updated estimates of potential evapotranspiration. In 2003, about 55,700 acre-feet of ground water was pumped in the DVRFS, of which 69 percent was used for irrigation, 13 percent for domestic, and 18 percent for public supply, commercial, and mining activities.

Dramatic inversion of charge polarity in diketopyrrolopyrrole-based organic field-effect transistors via a simple nitrile group substitution.

PubMed

Yun, Hui-Jun; Kang, Seok-Ju; Xu, Yong; Kim, Seul Ong; Kim, Yun-Hi; Noh, Yong-Young; Kwon, Soon-Ki

2014-11-19

A record-breaking high electron mobility of 7.0 cm(2) V(-1) s(-1) for n-channel polymer OFETs is reported. By the incorporation of only one nitrile group as an electron-withdrawing function in the vinyl linkage of the DPP-based copolymer, a dramatic inversion of majority charge-carriers from holes to electrons is achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Label-Free Proteomic Analysis of Protein Changes in the Striatum during Chronic Ethanol Use and Early Withdrawal

PubMed Central

Ayers-Ringler, Jennifer R.; Oliveros, Alfredo; Qiu, Yanyan; Lindberg, Daniel M.; Hinton, David J.; Moore, Raymond M.; Dasari, Surendra; Choi, Doo-Sup

2016-01-01

The molecular mechanisms underlying the neuronal signaling changes in alcohol addiction and withdrawal are complex and multifaceted. The cortico-striatal circuit is highly implicated in these processes, and the striatum plays a significant role not only in the early stages of addiction, but in the developed-addictive state as well, including withdrawal symptoms. Transcriptional analysis is a useful method for determining changes in gene expression, however, the results do not always accurately correlate with protein levels. In this study, we employ label-free proteomic analysis to determine changes in protein expression within the striatum during chronic ethanol use and early withdrawal. The striatum, composed primarily of medium spiny GABAergic neurons, glutamatergic and dopaminergic nerve terminals and astrocytes, is relatively homogeneous for proteomic analysis. We were able to analyze more than 5000 proteins from both the dorsal (caudate and putamen) and ventral (nucleus accumbens) striatum and identified significant changes following chronic intermittent ethanol exposure and acute (8 h) withdrawal compared to ethanol naïve and ethanol exposure groups respectively. Our results showed significant changes in proteins involved in glutamate and opioid peptide signaling, and also uncovered novel pathways including mitochondrial function and lipid/cholesterol metabolism, as revealed by changes in electron transport chain proteins and RXR activation pathways. These results will be useful in the development of novel treatments for alcohol withdrawal and thereby aid in recovery from alcohol use disorder. PMID:27014007

Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays.

PubMed

Boyd, S A; Sheng, G; Teppen, B J; Johnston, C T

2001-11-01

To more fully understand the potential for transport of nitroaromatic compounds in soils and subsoils,the adsorption of a series of para- and meta-substituted nitrobenzenes (SNBs) by K-smectite clay was measured. Adsorption isotherms were fit to the Freundlich equation, and the resultant Freundlich adsorption coefficients (log(Kf) were positively correlated with the Hammett substituent constant (r2 = 0.80). This relationship and a positive reaction constant (p = 1.15) indicate that the adsorption reaction is favored by electron-withdrawing substituents. These results are consistent with an electron donor (smectite)-acceptor (substituted nitrobenzene) mechanism offered previously. However, quantum calculations did not reveal any systematic relationship between the Hammett constant and the electron density on the aromatic ring, which would explain a donor-acceptor relationship. Rather, electron density donated by a second substituent on nitrobenzene appears to be appropriated by the nitro group leaving ring electron density unchanged. Fourier transform infrared spectroscopy revealed shifts in the -NO2 vibrational modes of 1,3,5-trinitrobenzene (TNB) upon adsorption to K+-smectite that were consistent with the complexation of K+ by -NO2 groups. Such TNB vibrational shifts were not observed for SWy-1 saturated with more strongly hydrated cations (i.e., Na+, Mg2+, Ca2+, and Ba2+). The simultaneous interaction of multiple -NO2 groups with exchangeable K+ was indicated by molecular dynamic simulations. Adsorption of SNBs by smectite clays appears to result from the additive interactions of -NO2 groups and secondary substituents with interlayer K+ ions. Adsorption occurs to a greater or lesser extent depending on the abilities of substituents to complex additional interlayer cations and the water solubilities of SNBs. We conclude that the adsorption trends of SNBs on K-SAz-1 can be explained without recourse to hypothetical electron donor-acceptor complexes.

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

Chan, A.; Tsiounis, Y.; Frankel, Y.

Recently, there has been an interest in making electronic cash protocols more practical for electronic commerce by developing e-cash which is divisible (e.g., a coin which can be spent incrementally but total purchases are limited to the monetary value of the coin). In Crypto`95, T. Okamoto presented the first practical divisible, untraceable, off-line e-cash scheme, which requires only O(log N) computations for each of the withdrawal, payment and deposit procedures, where N = (total coin value)/(smallest divisible unit). However, Okamoto`s set-up procedure is quite inefficient (on the order of 4,000 multi-exponentiations and depending on the size of the RSA modulus).more » The authors formalize the notion of range-bounded commitment, originally used in Okamoto`s account establishment protocol, and present a very efficient instantiation which allows one to construct the first truly efficient divisible e-cash system. The scheme only requires the equivalent of one (1) exponentiation for set-up, less than 2 exponentiations for withdrawal and around 20 for payment, while the size of the coin remains about 300 Bytes. Hence, the withdrawal protocol is 3 orders of magnitude faster than Okamoto`s, while the rest of the system remains equally efficient, allowing for implementation in smart-cards. Similar to Okamoto`s, the scheme is based on proofs whose cryptographic security assumptions are theoretically clarified.« less

Synthesis of novel disulfide and sulfone hybrid scaffolds as potent β-glucuronidase inhibitor.

PubMed

Taha, Muhammad; Ismail, Nor Hadiani; Imran, Syahrul; Wadood, Abdul; Rahim, Fazal; Al Muqarrabin, Laode Muhammad Ramadhan; Zaki, Hamizah Mohd; Ahmat, Norizan; Nasir, Abdul; Khan, Fahad

2016-10-01

Novel series of disulfide and sulfone hybrid analogs (1-20) were synthesized and characterized through EI-MS and (1)H NMR and evaluated for β-glucuronidase inhibitory potential. All synthesized analogs except 13 and 15 showed excellent β-glucuronidase inhibitory potential with IC50 value ranging in between 2.20-88.16μM as compared to standard d-saccharic acid 1,4 lactone (48.4±1.25μM). Analogs 19, 16, 4, 1, 17, 6, 10, 3, 18, 2, 11, 14 and 5 showed many fold potent activity against β-glucuronidase inhibitor. Structure activity relationship showed that substitution of electron withdrawing groups at ortho as well as para position on phenyl ring increase potency. Electron withdrawing groups at meta position on phenyl ring showed slightly low potency as compared to ortho and para position. The binding interactions were confirmed through molecular docking studies. Copyright © 2016 Elsevier Inc. All rights reserved.

Becoming Independent Storytellers: Modeling Children's Development of Narrative Macrostructure

ERIC Educational Resources Information Center

Kelly, Kimberly Reynolds; Bailey, Alison Louise

2013-01-01

For parents to provide effective support for their children's language development, they must be attuned to their child's changing abilities. This study presents a theoretically driven strategy that addresses a methodological challenge present when tracking longitudinally the cessation or "fading" of behaviors by capturing withdrawal of…

Efficacy of electronic cigarettes for smoking cessation.

PubMed

Orr, Katherine Kelly; Asal, Nicole J

2014-11-01

To review data demonstrating effective smoking cessation with electronic cigarettes (e-cigarettes). A literature search of MEDLINE/PubMed (1946-March 2014) was performed using the search terms e-cigarettes, electronic cigarettes, and smoking cessation. Additional references were identified from a review of literature citations. All English-language clinical studies assessing efficacy of e-cigarettes compared with baseline, placebo, or other pharmacological methods to aid in withdrawal symptoms, smoking reduction, or cessation were evaluated. A total of 6 clinical studies were included in the review. In small studies, e-cigarettes significantly decreased desire to smoke, number of cigarettes smoked per day, and exhaled carbon monoxide levels. Symptoms of nicotine withdrawal and adverse effects were variable. The most common adverse effects were nausea, headache, cough, and mouth/throat irritation. Compared with nicotine patches, e-cigarettes were associated with fewer adverse effects and higher adherence. Most studies showed a significant decrease in cigarette use acutely; however, long-term cessation was not sustained at 6 months. There is limited evidence for the effectiveness of e-cigarettes in smoking cessation; however, there may be a place in therapy to help modify smoking habits or reduce the number of cigarettes smoked. Studies available provided different administration patterns such as use while smoking, instead of smoking, or as needed. Short-term studies reviewed were small and did not necessarily evaluate cessation with a focus on parameters associated with cessation withdrawal symptoms. Though long-term safety is unknown, concerns regarding increased poisoning exposures among adults in comparison with cigarettes are alarming. © The Author(s) 2014.

Caffeine deprivation affects vigilance performance and mood.

PubMed

Lane, J D; Phillips-Bute, B G

1998-08-01

The effects of brief caffeine deprivation on vigilance performance, mood, and symptoms of caffeine withdrawal were studied in habitual coffee drinkers. Thirty male and female coffee drinkers were tested twice at midday (1130 to 1330 hours) after mornings in which they either consumed caffeinated beverages ad lib or abstained. Vigilance performance was tested with a 30-min computerized visual monitoring task. Mood and withdrawal symptom reports were collected by questionnaires. Caffeine deprivation was associated with impaired vigilance performance characterized by a reduction in the percentage of targets detected and an increase in response time, and by subjective reports of decreased vigor and increased fatigue and symptoms characterized by sleepiness, headache, and reduced ability to work. Even short periods of caffeine deprivation, equivalent in length to skipping regular morning coffee, can produce deficits in sustained attention and noticeable unpleasant caffeine-withdrawal symptoms in habitual coffee drinkers. Such symptoms may be a common side-effect of habitual caffeine consumption that contributes to the maintenance of this behavior.

Cumulative risk exposure moderates the association between parasympathetic reactivity and inhibitory control in preschool-age children.

PubMed

Giuliano, Ryan J; Roos, Leslie E; Farrar, Jessica D; Skowron, Elizabeth A

2018-04-01

A child's cumulative risk for early exposure to stress has been linked to alterations of self-regulation outcomes, including neurobiological correlates of inhibitory control (IC). We examined whether children's ability to engage the parasympathetic nervous system impacts how risk affects IC. Children ages 3-5 years completed two laboratory measures of IC while respiratory sinus arrhythmia (RSA) was measured, indexing parasympathetic activity. Children with greater risk demonstrated lower IC; risk also moderated associations between RSA reactivity and IC. For children with less risk, greater RSA withdrawal during IC tasks was associated with better IC. In contrast, greater risk was associated with poor IC, regardless of RSA withdrawal. Effects of risk were more pronounced for cumulative than individual measures. Results suggest that cumulative risk exposure disrupts connectivity between physiological and behavioral components of self-regulation in early childhood. Parasympathetic withdrawal to cognitive tasks may be less relevant for performance in developmental samples experiencing greater life stress. © 2018 Wiley Periodicals, Inc.

Progesterone receptor antagonist CDB-4124 increases depression-like behavior in mice without affecting locomotor ability

PubMed Central

Beckley, Ethan H.; Scibelli, Angela C.; Finn, Deborah A.

2010-01-01

Progesterone withdrawal has been proposed as an underlying factor in premenstrual syndrome and postpartum depression. Progesterone withdrawal induces forced swim test (FST) immobility in mice, a depression-like behavior, but the contribution of specific receptors to this effect is unclear. The role of progesterone’s GABAA receptor-modulating metabolite allopregnanolone in depression- and anxiety-related behaviors has been extensively documented, but little attention has been paid to the role of progesterone receptors. We administered the classic progesterone receptor antagonist mifepristone (RU-38486) and the specific progesterone receptor antagonist CDB-4124 to mice that had been primed with progesterone for five days, and found that both compounds induced FST immobility reliably, robustly, and in a dose-dependent fashion. Although CDB-4124 increased FST immobility, it did not suppress initial activity in a locomotor test. These findings suggest that decreased progesterone receptor activity contributes to depression-like behavior in mice, consistent with the hypothesis that progesterone withdrawal may contribute to the symptoms of premenstrual syndrome or postpartum depression. PMID:21163582

Environmental enrichment may protect against neural and behavioural damage caused by withdrawal from chronic alcohol intake.

PubMed

Nobre, Manoel Jorge

2016-12-01

Exposure to stress and prolonged exposure to alcohol leads to neuronal damages in several brain regions, being the medial prefrontal cortex (mPFC) one of the most affected. These changes presumably reduce the ability of the organism to cope with these stimuli and may underlie a series of maladaptive behaviours among which include drug addiction and withdrawal. Drug-addicted individuals show a pattern of behavior similar to patients with lesions of the mPFC. This impairment in the decision-making could be one of the mechanisms responsible for the transition from the casual to compulsive drug use. The environmental enrichment (EE) has a protective effect on the neural and cognitive impairments induced by psychoactive drugs, including ethyl alcohol. The present study aims to determine the influence of withdrawal from intermittent long-term alcohol exposure on alcohol preference, emotional reactivity and neural aspects of early isolated or grouped reared rats kept under standard or complex environments and the influence of social isolation on these measures, as well. Our results point out new insights on this matter showing that the EE can attenuate the adverse effects of withdrawal and social isolation on rat's behavior. This effect is probably due to its protective action on the mPFC integrity, including the cingulate area 1 (Cg1), and the prelimbic (PrL) and infralimbic cortex (IL), what could account for the absence of changes in the emotional reactivity in EE alcohol withdrawal rats. We argue that morphological changes at these cortical levels can afford the emotional, cognitive and behavioural dysregulations verified following withdrawal from chronic alcohol intake. Copyright © 2016 ISDN. Published by Elsevier Ltd. All rights reserved.

48 CFR 52.214-7 - Late submissions, modifications, and withdrawals of bids.

Code of Federal Regulations, 2010 CFR

2010-10-01

... transmitted through an electronic commerce method authorized by the IFB, it was received at the initial point... Government processes resume. (e) Bids may be withdrawn by written notice received at any time before the...

Performance Costs when Emotion Tunes Inappropriate Cognitive Abilities: Implications for Mental Resources and Behavior

ERIC Educational Resources Information Center

Storbeck, Justin

2012-01-01

Emotion tunes cognition, such that approach-motivated positive states promote verbal cognition, whereas withdrawal-motivated negative states promote spatial cognition (Gray, 2001). The current research examined whether self-control resources become depleted and influence subsequent behavior when emotion tunes an inappropriate cognitive tendency.…

REDUCED PERMEABILITY IN GROUNDWATER REMEDIATION SYSTEMS: ROLE OF MOBILIZED COLLOIDS AND INJECTED CHEMICALS

EPA Science Inventory

The success of pump-and-treat or in situ remediation of contaminated aquifers depends in part on the ability to maintain the permeability of the aquifer, withdrawal wells, and delivery systems at a reasonable cost while moving significant quantities of water. We have considered o...

Academic Disidentification, Race, and High School Dropouts

ERIC Educational Resources Information Center

Griffin, Bryan W.

2002-01-01

An important predictor of whether students remain in school or withdraw is their ability to identify with academics. Consistent with Ogbu's (1992) cultural inversion and Steele's (1992) stereotype threat hypotheses, research has shown that Black and Hispanic students tend to demonstrate higher levels of academic disidentification relative to Asian…

TRANSPORT AND SURVIVAL OF VIRUSES IN THE SUBSURFACE PROCESSES, EXPERIMENTS, AND SIMULATION MODELS

EPA Science Inventory

The remediation of ground water contaminated with waterborne pathogens, in particular with viruses, is based on their probable or actual ability to be transported from the source of origin to a point of withdrawal while maintaining the capacity to cause infections. The transport ...

Management of the geriatric trauma patient at risk of death: therapy withdrawal decision making.

PubMed

Trunkey, D D; Cahn, R M; Lenfesty, B; Mullins, R

2000-01-01

The management of geriatric injured patients admitted to a trauma center includes the selective decision to provide comfort care only, including withdrawal of therapy, and a choice to not use full application of standard therapies. The decision makers in this process include multiple individuals in addition to the patient. Retrospective review of documentation by 2 blinded reviewers of the cohort of patients over a recent 5-year period (1993-1997). Trauma service of a level I trauma center. A convenience sample of patients aged 65 years and older who died, and whose medical record was available for review. Patients were categorized as having withdrawal of therapy, and documentation in the medical record of who made the assessment decisions and recommendations, and to what extent the processes of care were documented. Among 87 geriatric trauma patients who died, 47 had documentation interpreted as indicating a decision was made to withdraw therapy. In only a few circumstances was the patient capable of actively participating in these decisions. The other individuals involved in recommendations for withdrawal of therapy were, in order of prevalence, the treating trauma surgeon, family members (as proxy reporting the patient's preferences), or a second physician. Documentation regarding the end-of-life decisions was often fragmentary, and in some cases ambiguous. Copies of legal advance directives were rarely available in the medical record, and ethics committee participation was used only once. Withdrawal of therapy is a common event in the terminal care of geriatric injured patients. The process for reaching a decision regarding withdrawal of therapy is complex because in most circumstances patients' injuries preclude their full participation. Standards for documentation of essential information, including patients' preferences and decision-making ability, should be developed to improve the process and assist with recording these complicated decisions that often occur over several days of discussion.

Design and synthesis of a new organic receptor and evaluation of colorimetric anion sensing ability in organo-aqueous medium

NASA Astrophysics Data System (ADS)

Srikala, P.; Tarafder, Kartick; Trivedi, Darshak R.

2017-01-01

A new organic receptor has been designed and synthesized by the combination of aromatic dialdehyde with nitro-substituted aminophenol resulting in a Schiff base compound. The receptor exhibited a colorimetric response for F- and AcO- ion with a distinct color change from pale yellow to red and pink respectively in dry DMSO solvent and yellow to pale greenish yellow in DMSO:H2O (9:1, v/v). UV-Vis titration studies displayed a significant shift in absorption maxima in comparison with the free receptor. The shift could be attributed to the hydrogen bonding interactions between the active anions and the hydroxyl functionality aided by the electron withdrawing nitro substituent on the receptor. 1H NMR titration and density functionality studies have been performed to understand the nature of interaction of receptor and anions. The lower detection limit of 1.12 ppm was obtained in organic media for F- ion confirming the real time application of the receptor.

Nicotine Withdrawal, Relapse of Mental Illness, or Medication Side-Effect? Implementing a Monitoring Tool for People With Mental Illness Into Quitline Counseling.

PubMed

Segan, Catherine J; Baker, Amanda L; Turner, Alyna; Williams, Jill M

2017-01-01

Smokers with mental illness and their health care providers are often concerned that smoking cessation will worsen mental health. Smokers with mental illness tend to be more nicotine-dependent and experience more severe symptoms of nicotine withdrawal, some of which are difficult to distinguish from psychiatric symptoms. In addition, smoking cessation can increase the blood levels and hence side effects of some psychotropic medications. Improved monitoring of nicotine withdrawal and medication side effects may help distinguish temporary withdrawal symptoms from psychiatric symptoms and facilitate targeted treatment to help smokers with mental illness manage the acute phase of nicotine withdrawal. The aim of this research was to examine the acceptability and feasibility to quitline counselors of implementing structured assessments of nicotine withdrawal and common medication side effects in people with mental illness who are quitting smoking using a telephone smoking cessation service. Monitoring involves administering (once pre-cessation and at each contact post-cessation) (1) the Minnesota Nicotine Withdrawal Scale, assessing eight symptoms: anger, anxiety, depression, cravings, difficulty concentrating, increased appetite, insomnia, and restlessness and (2) an adverse side effects checklist of 5 to 10 symptoms, for example, dry mouth and increased thirst. Following a 1-day update training in mental health, quitline counselors were asked to offer these assessments to callers disclosing mental illness in addition to usual counseling. Group interviews with counselors were conducted 2 months later to examine implementation barriers and benefits. Barriers included awkwardness in integrating a new structured practice into counseling, difficulty in limiting some callers to only the content of new items, and initial anxieties about how to respond to changes in some symptoms. Benefits included the ability to provide objective feedback on changes in symptoms, as this identified early benefits of quitting, provided reassurance for clients, and provided an opportunity for early intervention where symptoms worsened. Structured monitoring of withdrawal symptoms and medication side effects was able to be integrated into the quitline's counseling and was valued by counselors and clients. Given evidence of its benefits in this limited pilot study, we recommend it be considered for larger-scale adoption by quitlines.

Photochemical Synthesis of Complex Carbazoles: Evaluation of Electronic Effects in Both UV- and Visible-Light Methods in Continuous Flow.

PubMed

Hernandez-Perez, Augusto C; Caron, Antoine; Collins, Shawn K

2015-11-09

An evaluation of both a visible-light- and UV-light-mediated synthesis of carbazoles from various triarylamines with differing electronic properties under continuous-flow conditions has been conducted. In general, triarylamines bearing electron-rich groups tend to produce higher yields than triarylamines possessing electron-withdrawing groups. The incorporation of nitrogen-based heterocycles, as well as halogen-containing arenes in carbazole skeletons, was well tolerated, and often synthetically useful complementarity was observed between the UV-light and visible-light (photoredox) methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure-Property Relationships for Tailoring Phenoxazines as Reducing Photoredox Catalysts.

PubMed

McCarthy, Blaine G; Pearson, Ryan M; Lim, Chern-Hooi; Sartor, Steven M; Damrauer, Niels H; Miyake, Garret M

2018-04-18

Through the study of structure-property relationships using a combination of experimental and computational analyses, a number of phenoxazine derivatives have been developed as visible light absorbing, organic photoredox catalysts (PCs) with excited state reduction potentials rivaling those of highly reducing transition metal PCs. Time-dependent density functional theory (TD-DFT) computational modeling of the photoexcitation of N-aryl and core modified phenoxazines guided the design of PCs with absorption profiles in the visible regime. In accordance with our previous work with N, N-diaryl dihydrophenazines, characterization of noncore modified N-aryl phenoxazines in the excited state demonstrated that the nature of the N-aryl substituent dictates the ability of the PC to access a charge transfer excited state. However, our current analysis of core modified phenoxazines revealed that these molecules can access a different type of CT excited state which we posit involves a core substituent as the electron acceptor. Modification of the core of phenoxazine derivatives with electron-donating and electron-withdrawing substituents was used to alter triplet energies, excited state reduction potentials, and oxidation potentials of the phenoxazine derivatives. The catalytic activity of these molecules was explored using organocatalyzed atom transfer radical polymerization (O-ATRP) for the synthesis of poly(methyl methacrylate) (PMMA) using white light irradiation. All of the derivatives were determined to be suitable PCs for O-ATRP as indicated by a linear growth of polymer molecular weight as a function of monomer conversion and the ability to synthesize PMMA with moderate to low dispersity (dispersity less than or equal to 1.5) and initiator efficiencies typically greater than 70% at high conversions. However, only PCs that exhibit strong absorption of visible light and strong triplet excited state reduction potentials maintain control over the polymerization during the entire course of the reaction. The structure-property relationships established here will enable the application of these organic PCs for O-ATRP and other photoredox-catalyzed small molecule and polymer syntheses.

Construction and initial validation of the self-worth protection scale.

PubMed

Thompson, Ted; Dinnel, Dale L

2003-03-01

The self-worth theory of achievement motivation holds that in certain circumstances students stand to gain by deliberately withdrawing effort. When failure occurs despite effort, students are likely to conclude that failure resulted from lack of ability. Thus, withdrawing effort offers a defence against conclusions of low ability, thereby protecting self-worth. We undertook to assess the psychometric properties of the Self-Worth Protection Scale (SWPS). Data were obtained from 243 participants (Study 1) and 411 participants (Study 2) enrolled in undergraduate psychology courses at a university in the United States. We administered a number of scales, including the SWPS and scales assessing a fear of negative evaluation, academic self-esteem, uncertain global self-evaluations, self-handicapping, and causal uncertainty. Exploratory factor analysis indicated a three-factor solution (ability doubts, the importance of ability as a criterion of self-worth, and an avoidance orientation) utilising 33 of the original 44 items. A confirmatory factor analysis indicated that this three-factor solution was a poor fit of the data. After modifying the model, a confirmatory factor analysis indicated that a three-factor solution with 26 of the original items and a higher order factor of self-worth protection was an adequate fit of the data. Reliability measures were acceptable for the three subscales and total score. The total score of the SWPS was positively correlated with theoretically related constructs, demonstrating construct validity. The SWPS appears to be a psychometrically sound scale to assist in identifying individuals who manifest self-worth protection in achievement situations.

Molecular Engineering Strategy for High Efficiency Fullerene-Free Organic Solar Cells Using Conjugated 1,8-Naphthalimide and Fluorenone Building Blocks.

PubMed

Do, Thu Trang; Pham, Hong Duc; Manzhos, Sergei; Bell, John M; Sonar, Prashant

2017-05-24

We designed, synthesized, and characterized a series of novel electron deficient small molecule nonfullerene acceptors based on 1,8-naphthalimide (NAI) and 9-fluorenone (FN) with different branched alkyl chains using various techniques. These molecules are based on an acceptor-donor-acceptor-donor-acceptor (A1-D-A2-D-A1) molecular design configuration with NAI as the end-capping acceptor (A1), FN as electron-withdrawing central (A2) group, and thiophene ring as a donor (D) unit. These materials are named as NAI-FN-NAI (BO) and NAI-FN-NAI (HD) where BO and HD represent butyloctyl and hexyldecyl alkyl groups, respectively. To further modify energy levels of these materials, we converted the weak electron withdrawing ketonic group (C═O) attached to the FN moiety of NAI-FN-NAI (BO) to a stronger electron withdrawing cyano group (C≡N) to obtain the compound NAI-FCN-NAI (BO) by keeping the same alkyl chain. The optical, electrochemical, and thermal properties of the new acceptors were studied. The materials exhibited higher to medium band gaps, low lowest unoccupied molecular orbital (LUMO) energy levels, and highly thermally stable properties. Organic solar cell devices employing conventional poly(3-hexylthiophene) (P3HT) a donor polymer and the newly designed small molecules as the acceptor were investigated. Among all new materials, organic solar cell devices based on NAI-FN-NAI (BO) as an acceptor exhibit the highest performance with an open circuit voltage (V OC ) of 0.88 V, a short-circuit current density (J SC ) of 9.1 mAcm -2 , a fill factor (FF) of 45%, and an overall power conversion efficiency (PCE) of 3.6%. This is the first report of 9-fluorenone based nonfullerene acceptor with P3HT donor in organic solar cell devices with such a promising performance.

Role of Mathematics Learning Development Centres in HEIs

ERIC Educational Resources Information Center

Nzekwe-Excel, C.

2010-01-01

Background and Rationale: Student withdrawal and non-completion in institutions have been an issue of considerable concern. The lack of mathematical ability has been identified as a factor resulting to non-completion in higher institutions. Several students in higher education approach mathematics with a lot of anxiety. This has created the need…

The Emotional Impact of Pain on Children.

ERIC Educational Resources Information Center

Ozolins, Mickey S.; And Others

The inability of some children to cope with the pain from severe burns may result in depressive withdrawal or death. An understanding of the emotional impact of pain on children is essential to improve their ability to cope. A pilot project with seriously burned children employed three dependent measures to identify children who cope adaptively…

Acute electronic cigarette use: nicotine delivery and subjective effects in regular users.

PubMed

Dawkins, Lynne; Corcoran, Olivia

2014-01-01

Electronic cigarettes are becoming increasingly popular among smokers worldwide. Commonly reported reasons for use include the following: to quit smoking, to avoid relapse, to reduce urge to smoke, or as a perceived lower-risk alternative to smoking. Few studies, however, have explored whether electronic cigarettes (e-cigarettes) deliver measurable levels of nicotine to the blood. This study aims to explore in experienced users the effect of using an 18-mg/ml nicotine first-generation e-cigarette on blood nicotine, tobacco withdrawal symptoms, and urge to smoke. Fourteen regular e-cigarette users (three females), who are abstinent from smoking and e-cigarette use for 12 h, each completed a 2.5 h testing session. Blood was sampled, and questionnaires were completed (tobacco-related withdrawal symptoms, urge to smoke, positive and negative subjective effects) at four stages: baseline, 10 puffs, 60 min of ad lib use and a 60-min rest period. Complete sets of blood were obtained from seven participants. Plasma nicotine concentration rose significantly from a mean of 0.74 ng/ml at baseline to 6.77 ng/ml 10 min after 10 puffs, reaching a mean maximum of 13.91 ng/ml by the end of the ad lib puffing period. Tobacco-related withdrawal symptoms and urge to smoke were significantly reduced; direct positive effects were strongly endorsed, and there was very low reporting of adverse effects. These findings demonstrate reliable blood nicotine delivery after the acute use of this brand/model of e-cigarette in a sample of regular users. Future studies might usefully quantify nicotine delivery in relation to inhalation technique and the relationship with successful smoking cessation/harm reduction.

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

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS2 Nanosheets via Covalent Functionalization.

PubMed

Benson, Eric E; Zhang, Hanyu; Schuman, Samuel A; Nanayakkara, Sanjini U; Bronstein, Noah D; Ferrere, Suzanne; Blackburn, Jeffrey L; Miller, Elisa M

2018-01-10

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2 ) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3 CH 2 ) 2 NPh-MoS 2 ) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2 . The p-(CH 3 CH 2 ) 2 NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

Novel High Efficient Organic Photovoltaic Materials: Final Summary of Research

NASA Technical Reports Server (NTRS)

Sun, Sam

2002-01-01

The objectives and goals of this project were to investigate and develop high efficient, lightweight, and cost effective materials for potential photovoltaic applications, such as solar energy conversion or photo detector devices. Specifically, as described in the original project proposal, the target material to be developed was a block copolymer system containing an electron donating (or p-type) conjugated polymer block coupled to an electron withdrawing (or n-type) conjugated polymer block through a non-conjugated bridge unit. Due to several special requirements of the targeted block copolymer systems, such as electron donating and withdrawing substituents, conjugated block structures, processing requirement, stability requirement, size controllability, phase separation and self ordering requirement, etc., many traditional or commonly used block copolymer synthetic schemes are not suitable for this system. Therefore, the investigation and development of applicable and effective synthetic protocols became the most critical and challenging part of this project. During the entire project period, and despite the lack of a proposed synthetic polymer postdoctoral research associate due to severe shortage of qualified personnel in the field, several important accomplishments were achieved in this project and are briefly listed and elaborated. A more detailed research and experimental data is listed in the Appendix.

Tests and refinements of a general structure-activity model for avian repellents.

PubMed

Clark, L; Shah, P

1994-02-01

We tested the robustness of a structure-activity model for avian trigeminal chemoirritants. Fourteen benzoates and acetophenones were tested using European starlingsSturnus vulgaris as a bioassay. In general, the previously proposed model was a reasonable predictor of repellency (i.e., irritant potency). We found that the presence of a phenyl ring was critical to repellency. Basicity of the molecule is the next most critical feature influencing repellency. The presence of an acidic function within the electron-withdrawing functionality seriously detracts from repellency. The presence or absence of an electron-withdrawing or -donating group may potentiate repellent effects, but its presence is not critical, so long as the phenyl ring is electron rich. Our data suggest that there is ano-aminoacetophenone/methyl anthranilate trigeminal chemoreceptor in birds analogous to the mammalian capsaicin receptor. Both receptors contain a benzene site. However, birds seem to lack the associated thiol/hydrogen-bonding site present in mammals which is needed to activate the benzene site. Rather, birds may possess an associated exposed charged site that in turn may interact with the stimulus to activate the benzene site. These differences may explain the differential sensitivity of birds and mammals to aromatic irritants.

77 FR 65937 - Advisory Council to the Internal Revenue Service; Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-31

... Continuing to Balance Compliance and Tax Enforcement, Streamling the Audit Process, Managing Knowledge in the Issue Practice Groups and International Practice Networks, How Lien Withdrawal Processing should be made...) (Form 1040), Increase BMF Electronic Filing, Guidance Respecting Obligations of Tax Practitioner Under...

How to Submit a Risk Management Plan (RMP) to EPA

EPA Pesticide Factsheets

RMP*eSubmit software is the only way to submit RMPs. After you have prepared your plan using RMP*eSubmit, you may also re-submit, correct, or withdraw an RMP. Another electronic tool, RMP*Comp, performs the required off-site consequence analysis.

CC-1065 functional analogues possessing different electron-withdrawing substituents and leaving groups: synthesis, kinetics, and sequence specificity of reaction with DNA and biological evaluation.

PubMed

Wang, Y; Gupta, R; Huang, L; Lown, J W

1993-12-24

Antitumor agent CC-1065 functional analogues possessing different electron-withdrawing substituents and leaving groups have been synthesized. The extent and the relative rates of DNA cleavage following alkylation by these CPI structures and thermal treatment were determined independently by an ethidium binding assay and by agarose gel electrophoresis experiments. The anticipated preferential covalent binding to adenine sites within the minor groove was confirmed by sequencing determination of selected agents on high-resolution gels. Certain of the synthetic agents, unlike CC-1065, also bind covalently to G sites with weaker intensity. The cytotoxicities of these compounds were also determined against KB cells in vitro. Compounds bearing a bromo or nitro group in the benzene ring and a methylsulfonyl as a leaving group are 10 and 5 times more potent than their unsubstituted counterparts, respectively. Compounds bearing a methylsulfonyl as a leaving group are more potent than those bearing a chlorine.

Aryl sulfonate based anticancer alkylating agents.

PubMed

Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

2018-05-01

This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

All the World's a Stage: Integrating Theater and Medicine for Interprofessional Team Building in Physician and Nurse Residency Programs.

PubMed

Salam, Tabassum; Collins, Michelle; Baker, Ann-Marie

2012-01-01

To facilitate the delivery of excellent patient care, physician-nurse teams must work in a collaborative manner. We found that venues for the joint training of physician-nurse teams to foster collaboration are insufficient. We developed a novel interprofessional experience in which resident physicians and nurse residents practiced communication and collaboration skills involving a simulated alcohol withdrawal patient care scenario. Theater students portrayed the patients experiencing withdrawal. The team cared for each patient in a fully equipped and functioning hospital room in a simulation center. Together, they collaborated on interventions and a patient plan of care. After the 10-minute bedside scenario, physician and nurse educators facilitated a joint debriefing session for the physician-nurse learning team. Learners noted an improvement in their ability to identify alcohol withdrawal (44% of participants preencounter to 94% of participants postencounter) and to communicate with team members (55% of participants preencounter to 81% of participants postencounter). The learners felt the physician-nurse team training experience was exceptionally valuable for its authenticity.

Activators of potassium M currents have anticonvulsant actions in two rat models of encephalitis

PubMed Central

Solbrig, Marylou V.; Adrian, Russell; Wechsler, Steven L.; Koob, George F.

2010-01-01

Opioid systems in hippocampus regulate excitability and kappa opioids have a role in anticonvulsant protection, but their mechanisms of action are incompletely understood. We examined the ability of opioid and nonopioid agents with overlapping ionic mechanisms and actions similar to kappa opioid agonists, to block seizures in rat models of encephalitis due to Borna Disease virus and Herpes Simplex Virus Type-1. Naltrindole, a delta antagonist and thus a kappa opioid sparing agent, (10 mg/kg s.c.) blocked spontaneous and naloxone (opioid antagonist)-induced seizures in the models, but produced somatic signs similar to opioid withdrawal. Given that delta antagonists as well as kappa opioid agonists in hippocampus enhance potassium M currents (IM), we tested the effect of the IM augmenter flupirtine. Flupirtine (20 mg/kg i.p.) prevented seizures in Borna and herpes infected rats, without signs of withdrawal, hypotonia or sedation. The results support the efficacy of opioid and nonopioid drugs in modulating naloxone-induced seizures in critical illness due to viral encephalitis and by analogy, opioid withdrawal seizures. PMID:17126318

Progesterone receptor antagonist CDB-4124 increases depression-like behavior in mice without affecting locomotor ability.

PubMed

Beckley, Ethan H; Scibelli, Angela C; Finn, Deborah A

2011-07-01

Progesterone withdrawal has been proposed as an underlying factor in premenstrual syndrome and postpartum depression. Progesterone withdrawal induces forced swim test (FST) immobility in mice, a depression-like behavior, but the contribution of specific receptors to this effect is unclear. The role of progesterone's GABA(A) receptor-modulating metabolite allopregnanolone in depression- and anxiety-related behaviors has been extensively documented, but little attention has been paid to the role of progesterone receptors. We administered the classic progesterone receptor antagonist mifepristone (RU-38486) and the specific progesterone receptor antagonist CDB-4124 to mice that had been primed with progesterone for five days, and found that both compounds induced FST immobility reliably, robustly, and in a dose-dependent fashion. Although CDB-4124 increased FST immobility, it did not suppress initial activity in a locomotor test. These findings suggest that decreased progesterone receptor activity contributes to depression-like behavior in mice, consistent with the hypothesis that progesterone withdrawal may contribute to the symptoms of premenstrual syndrome or postpartum depression. Copyright © 2010 Elsevier Ltd. All rights reserved.

Design of aromatic-containing cell-penetrating peptide mimics with structurally modified π electronics.

PubMed

deRonde, Brittany M; Birke, Alexander; Tew, Gregory N

2015-02-09

Cell-penetrating peptides (CPPs) and their synthetic mimics (CPPMs) represent a class of molecules that facilitate the intracellular delivery of various cargo. Previous studies indicated that the presence of aromatic functionalities improved CPPM activity. Given that aromatic functionalities play prominent roles in membrane biology and participate in various π interactions, we explored whether these interactions could be optimized for improved CPPM activity. CPPMs were synthesized by ring-opening metathesis polymerization by using monomers that contained aromatic rings substituted with electron-donating and electron-withdrawing groups and covered an electrostatic potential range from -29.69 to +15.57 kcal mol(-1) . These groups altered the quadrupole moments of the aromatic systems and were used to test if such structural modifications changed CPPM activity. CPPMs were added to dye-loaded vesicles and the release of carboxyfluorescein was monitored as a function of polymer concentration. Changes in the effective polymer concentration to release 50% of the dye (effective concentration, EC50 ) were monitored. Results from this assay showed that the strength of the electron-donating and electron-withdrawing groups incorporated in the CPPMs did not alter polymer EC50 values or activity. This suggests that other design parameters may have a stronger impact on CPPM activity. In addition, these results indicate that a wide range of aromatic groups can be incorporated without negatively impacting polymer activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Problems with Current Models of Grieving and Consequences for Older Persons.

ERIC Educational Resources Information Center

Horacek, Bruce J.

Classical models of the grieving process include Freud's concept of withdrawal of ties to the love object called decathexis, and Lindemann's emancipation from the bondage to the deceased involving adjusting to the loss in one's environment and the ability to form new relationships. Most of the models and explanations of the grieving process over…

Parent Use of DRI on High Rate Disruptive Behavior: Direct and Collateral Benefits.

ERIC Educational Resources Information Center

Friman, Patrick C.; Altman, Karl

1990-01-01

This study evaluates parental use of differential reinforcement of other and/or incompatible behavior to treat high-rate disruptive behavior in a severely retarded four-year-old boy. A withdrawal experimental design was used. Intervention effectively reduced instances of toy chewing and throwing, while appropriate toy play and ability to remain…

Variant and Invariant Predictors of Perceived Popularity across Majority-Black and Majority-White Classrooms

ERIC Educational Resources Information Center

Meisinger, E. B.; Blake, J. J.; Lease, A. M.; Palardy, G. J.; Olejnik, S. F.

2007-01-01

Behavioral descriptors were identified as variant or invariant predictors of perceived popularity in a sample of 516 fourth, fifth, and sixth grade children located in 26 majority-Black or majority-White classrooms. Athletic ability, prosocial behavior, being "cool", social withdrawal, and "personal privilege" (i.e., having a lot of expensive…

Addressing the Problem of Poorly Preserved Zoological Specimens: A Case Study with Turtles

ERIC Educational Resources Information Center

Thomas, Robert A.; Thomas, Aimée K.

2015-01-01

We present a new use for a poorly preserved turtle specimen that teachers can easily use in demonstrating vertebrate anatomy or adaptive herpetology at the high school or college level. We give special attention to illustrating the sigmoid flexure of the neck as certain turtles withdraw their heads. This ability is anatomically and biologically…

Metal complexes of substituted Gable porphyrins as oxidation catalysts

DOEpatents

Lyons, James E.; Ellis, Jr., Paul E.; Wagner, Richard W.

1996-01-01

Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

15 CFR 335.5 - Licenses.

Code of Federal Regulations, 2011 CFR

2011-01-01

... importer as suitable for use in making suits, suit-type jackets, or trousers under the appropriate Tariff... (Customs Form 7501). (f) A Licensee may only authorize an importer to import fabric under the license on... the entry summary or warehouse withdrawal for consumption (Customs Form 7501), or its electronic...

15 CFR 335.5 - Licenses.

Code of Federal Regulations, 2012 CFR

2012-01-01

... importer as suitable for use in making suits, suit-type jackets, or trousers under the appropriate Tariff... (Customs Form 7501). (f) A Licensee may only authorize an importer to import fabric under the license on... the entry summary or warehouse withdrawal for consumption (Customs Form 7501), or its electronic...

15 CFR 335.5 - Licenses.

Code of Federal Regulations, 2013 CFR

2013-01-01

... importer as suitable for use in making suits, suit-type jackets, or trousers under the appropriate Tariff... (Customs Form 7501). (f) A Licensee may only authorize an importer to import fabric under the license on... the entry summary or warehouse withdrawal for consumption (Customs Form 7501), or its electronic...

15 CFR 335.5 - Licenses.

Code of Federal Regulations, 2014 CFR

2014-01-01

... importer as suitable for use in making suits, suit-type jackets, or trousers under the appropriate Tariff... (Customs Form 7501). (f) A Licensee may only authorize an importer to import fabric under the license on... the entry summary or warehouse withdrawal for consumption (Customs Form 7501), or its electronic...

Demonstration optimization analyses of pumping from selected Arapahoe aquifer municipal wells in the west-central Denver Basin, Colorado, 2010–2109

USGS Publications Warehouse

Banta, Edward R.; Paschke, Suzanne S.

2012-01-01

Declining water levels caused by withdrawals of water from wells in the west-central part of the Denver Basin bedrock-aquifer system have raised concerns with respect to the ability of the aquifer system to sustain production. The Arapahoe aquifer in particular is heavily used in this area. Two optimization analyses were conducted to demonstrate approaches that could be used to evaluate possible future pumping scenarios intended to prolong the productivity of the aquifer and to delay excessive loss of saturated thickness. These analyses were designed as demonstrations only, and were not intended as a comprehensive optimization study. Optimization analyses were based on a groundwater-flow model of the Denver Basin developed as part of a recently published U.S. Geological Survey groundwater-availability study. For each analysis an optimization problem was set up to maximize total withdrawal rate, subject to withdrawal-rate and hydraulic-head constraints, for 119 selected municipal water-supply wells located in 96 model cells. The optimization analyses were based on 50- and 100-year simulations of groundwater withdrawals. The optimized total withdrawal rate for all selected wells for a 50-year simulation time was about 58.8 cubic feet per second. For an analysis in which the simulation time and head-constraint time were extended to 100 years, the optimized total withdrawal rate for all selected wells was about 53.0 cubic feet per second, demonstrating that a reduction in withdrawal rate of about 10 percent may extend the time before the hydraulic-head constraints are violated by 50 years, provided that pumping rates are optimally distributed. Analysis of simulation results showed that initially, the pumping produces water primarily by release of water from storage in the Arapahoe aquifer. However, because confining layers between the Denver and Arapahoe aquifers are thin, in less than 5 years, most of the water removed by managed-flows pumping likely would be supplied by depleting overlying hydrogeologic units, substantially increasing the rate of decline of hydraulic heads in parts of the overlying Denver aquifer.

Assessing colonoscopic inspection skill using a virtual withdrawal simulation: a preliminary validation of performance metrics.

PubMed

Zupanc, Christine M; Wallis, Guy M; Hill, Andrew; Burgess-Limerick, Robin; Riek, Stephan; Plooy, Annaliese M; Horswill, Mark S; Watson, Marcus O; de Visser, Hans; Conlan, David; Hewett, David G

2017-07-12

The effectiveness of colonoscopy for diagnosing and preventing colon cancer is largely dependent on the ability of endoscopists to fully inspect the colonic mucosa, which they achieve primarily through skilled manipulation of the colonoscope during withdrawal. Performance assessment during live procedures is problematic. However, a virtual withdrawal simulation can help identify and parameterise actions linked to successful inspection, and offer standardised assessments for trainees. Eleven experienced endoscopists and 18 endoscopy novices (medical students) completed a mucosal inspection task during three simulated colonoscopic withdrawals. The two groups were compared on 10 performance metrics to preliminarily assess the validity of these measures to describe inspection quality. Four metrics were related to aspects of polyp detection: percentage of polyp markers found; number of polyp markers found per minute; percentage of the mucosal surface illuminated by the colonoscope (≥0.5 s); and percentage of polyp markers illuminated (≥2.5 s) but not identified. A further six metrics described the movement of the colonoscope: withdrawal time; linear distance travelled by the colonoscope tip; total distance travelled by the colonoscope tip; and distance travelled by the colonoscope tip due to movement of the up/down angulation control, movement of the left/right angulation control, and axial shaft rotation. Statistically significant experienced-novice differences were found for 8 of the 10 performance metrics (p's < .005). Compared with novices, experienced endoscopists inspected more of the mucosa and detected more polyp markers, at a faster rate. Despite completing the withdrawals more quickly than the novices, the experienced endoscopists also moved the colonoscope more in terms of linear distance travelled and overall tip movement, with greater use of both the up/down angulation control and axial shaft rotation. However, the groups did not differ in the number of polyp markers visible on the monitor but not identified, or movement of the left/right angulation control. All metrics that yielded significant group differences had adequate to excellent internal consistency reliability (α = .79 to .90). These systematic differences confirm the potential of the simulated withdrawal task for evaluating inspection skills and strategies. It may be useful for training, and assessment of trainee competence.

Comparative Evaluation of Partial α2 -Adrenoceptor Agonist and Pure α2 -Adrenoceptor Antagonist on the Behavioural Symptoms of Withdrawal after Chronic Alcohol Administration in Mice.

PubMed

Arora, Shivani; Vohora, Divya

2016-08-01

As an addictive drug, alcohol produces withdrawal symptoms if discontinued abruptly after chronic use. Clonidine (CLN), a partial α2 -adrenergic agonist, and mirtazapine (MRT), an antagonist of α2 -adrenoceptor, both clinically aid alcohol withdrawal. Considering different mechanisms of action of the two drugs, this study was designed to see how far these two mechanistically different drugs differ in their ability to decrease the severity of ethanol withdrawal syndrome. The effect of CLN and MRT on ethanol withdrawal-induced anxiety, depression and memory impairment was analysed using EPM, FST and PAR tests, respectively. Animals received distilled water, ethanol and/or either of the drugs (CLN and MRT) in different doses. Relapse to alcohol use was analysed by CPP test. Animals received ethanol as a conditioning drug and distilled water, CLN or MRT as test drug. CLN and MRT both alleviated anxiety in a dose-dependent manner. MRT (4 mg/kg) was more effective than CLN (0.1 mg/kg) in ameliorating the anxiogenic effect of alcohol withdrawal. However, CLN treatment increased depression. It significantly decreased swimming time and increased immobility time, whereas MRT treatment decreased immobility time and increased climbing and swimming time during abstinence. The effect was dose dependent for both drugs. The results of PAR test show that CLN treatment worsens working memory. Significant increase in SDE and TSZ and decrease in SDL were observed in CLN-treated animals. MRT treatment, on the other hand, improved working memory at both doses. Further, both CLN and MRT alleviated craving. A significant decrease in time spent in the ethanol-paired chamber was seen. MRT treatment at both doses showed better effect than CLN in preventing the development of preference in CPP test. These findings indicate a potential therapeutic use and better profile of mirtazapine over clonidine in improving memory, as well as in alleviating depression, anxiety and craving associated with alcohol withdrawal. © 2016 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

Theoretical Study of Electron Transfer Properties of Squaraine Dyes for Dye Sensitized Solar Cell

NASA Astrophysics Data System (ADS)

Juwita, Ratna; Tsai, Hui-Hsu Gavin

2018-01-01

The environmental issues and high cost of Ru create many scientists to explore cheaper and safer sensitizer as alternative for dye sensitized solar cells (DSCs). Dyes play an important role in solar energy conversion efficiency. The squaraine (SQ) dyes has good spectral match with the solar spectra, therefore, SQ dyes have great potential for the applications in DSCs. SQ01_CA is an unsymmetrical SQ dye, reported by Grätzel and colleagues in 2007, featuring a D-π-spacer-A framework and has a carboxylic acid anchoring group. The electron donating ability of indolium in SQ01_CA and SQ01_CAA dyes is relatively weak, better performance may be achieved by introducing an additional donor moiety into indolium [1]. In this study, we investigate six unsymmetrical SQ dyes adsorbed on a (TiO2)38 cluster [2] using density functional theory (DFT) and time-dependent DFT to study electron transfer properties of squaraine dyes on their photophysical. SQ01_CA, WH-SQ01_CA, and WH-SQ02_CA use a carboxylic acid group as its electron acceptor. Furthermore, SQ01_CAA, WH-SQ01_CAA, and WH-SQ02_CAA use a cyanoacrylic acid group as its electron acceptor. WH-SQ01_CA and WH-SQ01_CAA have an alkyl, while WH-SQ02_CA and WH-SQ02_CAA have alkoxyl substituted diarylamines to the indolium donor of sensitizer SQ01_CA. Our calculations show with additional diarylamines in donor tail of WH-SQ02_CAA, the SQ dyes have red-shifted absorption and have slightly larger probability of electron density transferred to TiO2 moiety. Furthermore, an additional -CN group as electron a withdrawing group in the acceptor exhibits red-shifted absorption and enhances the electron density transferred to TiO2 and anchoring moiety after photo-excitation. The tendency of calculated probabilities of electron density being delocalized into TiO2 and driving force for excited-state electron injection of these studied SQ dyes is compatible with their experimentally observed.

One-pot, two-step desymmetrization of symmetrical benzils catalyzed by the methylsulfinyl (dimsyl) anion.

PubMed

Ragno, Daniele; Bortolini, Olga; Giovannini, Pier Paolo; Massi, Alessandro; Pacifico, Salvatore; Zaghi, Anna

2014-08-14

An operationally simple one-pot, two-step procedure for the desymmetrization of benzils is herein described. This consists in the chemoselective cross-benzoin reaction of symmetrical benzils with aromatic aldehydes catalyzed by the methyl sulfinyl (dimsyl) anion, followed by microwave-assisted oxidation of the resulting benzoylated benzoins with nitrate, avoiding the costly isolation procedure. Both electron-withdrawing and electron-donating substituents may be accommodated on the aromatic rings of the final unsymmetrical benzil.

Reactivity measurement in estimation of benzoquinone and benzoquinone derivatives’ allergenicity

PubMed Central

Mbiya, Wilbes; Chipinda, Itai; Simoyi, Reuben H.; Siegel, Paul D.

2015-01-01

Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking. PMID:26612505

Electronic structure and fragmentation properties of [Fe4S4(SEt)4-x(SSEt)x]2-

NASA Astrophysics Data System (ADS)

Fu, You-Jun; Laskin, Julia; Wang, Lai-Sheng

2007-06-01

A limited exposure of (n-Bu4N)2[Fe4S4(SEt)4] solutions in acetonitrile to air was found to produce a new series of [4Fe-4S] cluster complexes, [Fe4S4(SEt)4-x(SSEt)x]2- (x = 1-4), with the original -SEt ligands substituted by -SSEt di-sulfide ligands, which were formed due to partial decomposition of the [4Fe-4S] core in parent [Fe4S4(SEt)4]2-. The products were first observed in the experiments with an ESI-ion Trap-TOF mass spectrometer and were further identified using high resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Photoelectron spectra of the [Fe4S4(SEt)4-x(SSEt)x]2- dianions revealed that the -SSEt coordination induced little change in the electronic structure of the [4Fe-4S] cluster, but the electron binding energies of [Fe4S4(SEt)4-x(SSEt)x]2- increased from 0.52 to 0.73 eV with increase in x from 0 to 4, suggesting a greater electron withdrawing ability of -SSEt than -SEt. In high resolution MS/MS experiments on [Fe4S4(SEt)3(SSEt)]2-/1-, clusters with both charge states yielded fragment [Fe4S4(SEt)3]-, suggesting that -SSEt could be lost either as a negatively charged ion SSEt- from the doubly charged precursor, or as a radical SSEt from the singly charged species. The biological implication of the interaction between [Fe4S4(SEt)4]2- and O2 is discussed in comparison to the air exposure of [4Fe-4S] proteins to the air.

Synthetic substrates for enzyme analysis

DOEpatents

Bissell, E.R.; Mitchell, A.R.; Pearson, K.W.; Smith, R.E.

1983-06-14

Synthetic substrates are provided which may be represented as A-D. The A moiety includes an amino acid, polypeptide, or derivative. The D moiety includes 7-amino coumarin derivatives having an electron withdrawing substituent group at the 3 position carbon or fused between the 3 and 4 position carbons. No Drawings

Metal complexes of substituted Gable porphyrins as oxidation catalysts

DOEpatents

Lyons, J.E.; Ellis, P.E. Jr.; Wagner, R.W.

1996-01-02

Transition metal complexes of Gable porphyrins are disclosed having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

Synthetic substrates for enzyme analysis

DOEpatents

Bissell, Eugene R.; Mitchell, Alexander R.; Pearson, Karen W.; Smith, Robert E.

1983-01-01

Synthetic substrates are provided which may be represented as A-D. The A moiety thereof includes an amino acid, polypeptide, or derivative thereof. The D moiety thereof includes 7-amino coumarin derivatives having an electron withdrawing substituent group at the 3 position carbon or fused between the 3 and 4 position carbons.

Space, agency, and withdrawal: birth control choices of women in Turkey.

PubMed

Sirkeci, Ibrahim; Cindoglu, Dilek

2012-01-01

Withdrawal (WD) is not a reliable method for preventing unwanted pregnancies, yet it is still a very popular form of birth control in many societies, including Turkey. We look at the relationship between women's agency and physical space in relation to birth control choices of women in Turkey. Agency in our context refers to a woman's ability to resist domination and subordination to the patriarchal beliefs valuing her reproductivity over her pleasure. Our analysis of the Turkish Demographic Health Survey (TDHS) suggests that (a) the available space in the household for possible private encounters between husband and wife, and (b) the women's capacity to insert her agency into her life choices are closely correlated with WD choices. Women with better social and physical resources prefer WD less.

/sup 13/C NMR spectra of cyclic nitrones. 2. 1- and 4-substituted 2,2,5,5-tetramethyl-3-imidazoline 3-oxides

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

Grigor'ev, I.A.; Shchukin, G.I.; Martin, V.V.

1985-08-01

The chemical shift of the carbon atom of the nitrone group in the /sup 13/C NMR spectra of 3-imidazoline 3-oxides lies in the region of 117-152 ppm and depends on the electronic effect of the substituents at positions 1, 4, and 5 of the heterocycle. Increase in the electron-withdrawing character of the substituent at these positions leads to an upfield shift of the signal for the nitrone carbon atom, and this corresponds to the increase in electron density on it.

A randomised, crossover study on an electronic vapour product, a nicotine inhalator and a conventional cigarette. Part B: Safety and subjective effects.

PubMed

Walele, Tanvir; Sharma, Girish; Savioz, Rebecca; Martin, Claire; Williams, Josie

2016-02-01

An Electronic Vapour Product (EVP) has been evaluated for short-term safety parameters and subjective effects in a 2-part study, in smokers. Part 1 compared the EVP with unflavoured (UF) and flavoured (FL) e-liquid at 2.0% nicotine to a conventional cigarette (CC; JPS Silver King Size, 0.6 mg) and a licensed nicotine inhalator (Nicorette(®), 15 mg). Part 2 assessed the effect of increasing concentrations of nicotine in the e-liquid used with the EVP (0%, 0.4%, 0.9%, 2.0%). The study was designed as a randomised, controlled, crossover trial. Outcomes included adverse events (AEs), vital signs, exhaled carbon monoxide (CO), clinical laboratory parameters, smoking urges and withdrawal symptoms. In both study parts, only mild non-serious AEs were reported. No major differences were observed in AEs between the EVPs and Nicorette(®). Exhaled CO levels only increased for CC. All products appeared to decrease smoking urges and nicotine withdrawal symptom scores to a similar extent. The EVP had a similar short-term safety profile to Nicorette(®) and relieved smoking urges and nicotine withdrawal symptoms to a similar extent as Nicorette(®) and CC. Unlike nicotine replacement therapies, the EVP may offer an alternative for those finding it difficult to quit the behavioural and sensorial aspects of smoking. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

The use-dependent, nicotinic antagonist BTMPS reduces the adverse consequences of morphine self-administration in rats in an abstinence model of drug seeking

PubMed Central

Hall, Brandon J.; Pearson, Laura S.; Terry, Alvin V.; Buccafusco, Jerry J.

2011-01-01

In this study, the use-dependent, nicotinic receptor antagonist bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) sebacate (BTMPS) was evaluated for its ability to attenuate the adverse consequences associated with morphine in rats in all three phases of an abstinence model of drug seeking: self-administration, acute withdrawal, and delayed test of drug seeking. Rats were allowed to self-administer morphine (FR1 schedule) with an active response lever, on a 24hr basis inside operant chambers, for 14 days. Each rat was subsequently evaluated for stereotypical behaviors associated with spontaneous morphine withdrawal. Rats were then placed in standard housing cages for a six week period of protracted abstinence from morphine. After this period, each rat was placed back into its respective operant chamber for a 14 day assessment of unrewarded drug seeking responses. BTMPS was administered to the animals in all three clinically relevant phases in three separate sets of experiments. BTMPS treatment during the self-administration phase resulted in up to a 34% reduction of lever responses to morphine when compared to vehicle treated control animals, as well as a 32% reduction in the dose of morphine self-administered. When given during self-administration and acute withdrawal, BTMPS treatment decreased acute withdrawal symptoms (up to 64%) of morphine use and reduced (up to 45%) drug seeking responses after six weeks of protracted withdrawal compared to control animals. BTMPS treatment after six weeks of abstinence from morphine had no effect. These results offer insight into the role of central cholinergic receptors in the onset and maintenance of drug addiction. PMID:21651919

Asymmetrical squaraines for high-performance small-molecule organic solar cells with a short circuit current of over 12 mA cm(-2).

PubMed

Chen, Yao; Zhu, Youqin; Yang, Daobin; Luo, Qian; Yang, Lin; Huang, Yan; Zhao, Suling; Lu, Zhiyun

2015-04-11

An asymmetrical squaraine dye (Py-3) with its two electron-donating aryl groups directly linked to the electron-withdrawing squaric acid core possesses an ideal bandgap of 1.33 eV, together with an intense and broad absorption band in the range 550-950 nm. Hence, the resulting solution-processed solar cells display an impressive Jsc of 12.03 mA cm(-2) and a PCE of 4.35%.

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

Park Y. S.; Kale, T.; Wu, Q.

A series of diketopyrrolopyrrole(DPP)-based small molecules have been synthesized by palladium-catalyzed coupling reactions. Electron-donating moieties (benzothiophene, benzoselenophene, and benzotellurophene) are bridged by an electron-withdrawing DPP unit to generate donor-acceptor-donor (D-A-D) type molecules. We observe red-shifts in absorption spectra of these compounds by varying heteroatoms from sulfur to tellurium. In bulk heterojunction solar cells with [6,6]phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor, we obtain power conversion efficiencies of 2.4% (benzothiophene), 4.1% (benzoselenophene), and 3.0% (benzotellurophene), respectively.

Antimalarial Activity of C-10 Substituted Triazolyl Artemisinin.

PubMed

Park, Gab-Man; Park, Hyun; Oh, Sangtae; Lee, Seokjoon

2017-12-01

We synthesized C-10 substituted triazolyl artemisinins by the Huisgen cycloaddition reaction between dihydroartemisinins (2) and variously substituted 1, 2, 3-triazoles (8a-8h). The antimalarial activities of 32 novel artemisinin derivatives were screened against a chloroquine-resistant parasite. Among them, triazolyl artemisinins with electron-withdrawing groups showed stronger antimalarial activities than those shown by the derivatives having electron-donating groups. In particularly, m-chlorotriazolyl artemisinin (9d-12d) showed antimalarial activity equivalent to that of artemisinin and could be a strong drug candidate.

Microwave-Assisted Organocatalytic Intramolecular Knoevenagel/Hetero Diels-Alder Reaction with O-(Arylpropynyloxy)-Salicylaldehydes: Synthesis of Polycyclic Embelin Derivatives.

PubMed

Martín-Acosta, Pedro; Feresin, Gabriela; Tapia, Alejandro; Estévez-Braun, Ana

2016-10-21

A highly efficient and regioselective approach to new polycyclic embelin derivatives through a domino Knoevenagel condensation/intramolecular hetero Diels-Alder reaction using O-(arylpropynyloxy)-salicylaldehydes in the presence of ethylenediamine diacetate (EDDA) is reported. This organocatalyzed protocol is compatible toward a wide range of aryl-substituted alkynyl ethers with electron-donating and electron-withdrawing groups. When other active methylene compounds were subjected to this domino reaction the corresponding adducts were obtained in high yield.

Substituent effects in infrared spectroscopy—VII. Meta and para substituted methanesulphonanilides

NASA Astrophysics Data System (ADS)

Laurence, C.; Berthelot, M.; Lucon, M.; Tsuno, Y.

Substituent effects on the NH frequencies of the conformers of methanesulphonanilides, their cyclic dimers and their hydrogen bonded complexes with acetonitrile have been analysed by means of the Hammet equation. An electron-withdrawing substituent may either increase or decrease ν(NH) in the XC 6H 4NHY series according to the electronic nature of the Y group. This can be explained by the non-monotonic dependence of the NH stretching frequency on the ionic character of the NH bond.

A Simple Base-Mediated Halogenation of Acidic sp2 C-H Bonds under Non-Cryogenic Conditions

PubMed Central

Do, Hien-Quang; Daugulis, Olafs

2009-01-01

A new method has been developed for in situ halogenation of acidic sp2 carbon-hydrogen bonds in heterocycles and electron-deficient arenes. Either selective monohalogenation or one-step exhaustive polyhalogenation is possible for substrates possessing several C-H bonds that are flanked by electron-withdrawing groups. For the most acidic arenes, such as pentafluorobenzene, K3PO4 base can be employed instead of BuLi for metalation/halogenation sequences. PMID:19102661

Poor Performance in Mathematics: Is There a Basis for a Self-Worth Explanation for Women?

ERIC Educational Resources Information Center

Thompson, Ted; Dinnel, Dale L.

2007-01-01

The self-worth theory of achievement motivation holds that in situations in which poor performance is likely to reveal low ability, certain students (known as self-worth protective students) intentionally withdraw effort in order to avoid the negative implications of poor performance in terms of damage to self-worth. In this study, evidence of…

On the Leaky Math Pipeline: Comparing Implicit Math-Gender Stereotypes and Math Withdrawal in Female and Male Children and Adolescents

ERIC Educational Resources Information Center

Steffens, Melanie C.; Jelenec, Petra; Noack, Peter

2010-01-01

Many models assume that habitual human behavior is guided by spontaneous, automatic, or implicit processes rather than by deliberate, rule-based, or explicit processes. Thus, math-ability self-concepts and math performance could be related to implicit math-gender stereotypes in addition to explicit stereotypes. Two studies assessed at what age…

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice

PubMed Central

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal. PMID:26962395

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice.

PubMed

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal.

Electrophilic Triterpenoid Enones: A Comparative Thiol-Trapping and Bioactivity Study.

PubMed

Del Prete, Danilo; Taglialatela-Scafati, Orazio; Minassi, Alberto; Sirignano, Carmina; Cruz, Cristina; Bellido, Maria L; Muñoz, Eduardo; Appendino, Giovanni

2017-08-25

Bardoxolone methyl (1) is the quintessential member of triterpenoid cyanoacrylates, an emerging class of bioactive compounds capable of transient covalent binding to thiols. The mechanistic basis for this unusual "pulsed reactivity" profile and the mode of its biological translation are unknown. To provide clues on these issues, a series of Δ 1 -dehydrooleanolates bearing an electron-withdrawing group at C-2 (7a-m) were prepared from oleanolic acid (3a) and comparatively investigated in terms of reactivity with thiols and bioactivity against a series of electrophile-sensitive transcription factors (Nrf2, NF-κB, STAT3). The emerging picture suggests that the triterpenoid scaffold sharply decreases the reactivity of the enone system by steric encumbrance and that only strongly electrophilic and sterically undemanding substituents such as a cyanide or a carboxylate group can re-establish Michael reactivity, albeit in a transient way for the cyanide group. In general, a substantial dissection between the thiol-trapping ability and the modulation of biological end-points sensitive to thiol alkylation was observed, highlighting the role of shape complementarity for the activity of triterpenoid thia-Michael acceptors.

Design, synthesis of novel chitosan derivatives bearing quaternary phosphonium salts and evaluation of antifungal activity.

PubMed

Tan, Wenqiang; Zhang, Jingjing; Luan, Fang; Wei, Lijie; Chen, Yuan; Dong, Fang; Li, Qing; Guo, Zhanyong

2017-09-01

Two novel chitosan derivatives modified with quaternary phosphonium salts were successfully synthesized, including tricyclohexylphosphonium acetyl chitosan chloride (TCPACSC) and triphenylphosphonium acetyl chitosan chloride (TPPACSC), and characterized by FTIR, 1 H NMR, and 13 C NMR spectra. The degree of substitution was also calculated by elemental analysis results. Their antifungal activities against Colletotrichum lagenarium, Watermelon fusarium, and Fusarium oxysporum were investigated in vitro using the radial growth assay, minimal inhibitory concentration, and minimum bactericidal concentration assay. The fungicidal assessment revealed that the synthesized chitosan derivatives had superior antifungal activity compared with chitosan. Especially, TPPACSC exhibited the best antifungal property with inhibitory indices of over 75% at 1.0mg/mL. The results obviously showed that quaternary phosphonium groups could effectively enhance antifungal activity of the synthesized chitosan derivatives. Meanwhile, it was also found that their antifungal activity was influenced by electron-withdrawing ability of the quaternary phosphonium salts. The synthetic strategy described here could be utilized for the development of chitosan as antifungal biomaterials. Copyright © 2017 Elsevier B.V. All rights reserved.

Modification of D-A-π-A configuration toward a high-performance triphenylamine-based sensitizer for dye-sensitized solar cells: a theoretical investigation.

PubMed

Tarsang, Ruangchai; Promarak, Vinich; Sudyoadsuk, Taweesak; Namuangruk, Supawadee; Kungwan, Nawee; Jungsuttiwong, Siriporn

2014-12-01

In an attempt to shed light on how the addition of a benzothiadiazole (BTD) moiety influences the properties of dyes, a series of newly designed triphenylamine-based sensitizers incorporating a BTD unit as an additional electron-withdrawing group in a specific donor-acceptor-π-acceptor architecture has been investigated. We found that different positions of the BTD unit provided significantly different responses for light absorption. Among these, it was established that the further the BTD unit is away from the donor part, the broader the absorption spectra, which is an observation that can be applied to improve light-harvesting ability. However, when the BTD unit is connected to the anchoring group a faster, unfavorable charge recombination takes place; therefore, a thiophene unit was inserted between these two acceptors, providing redshifted absorption spectra as well as blocking unfavorable charge recombination. The results of our calculations provide valuable information and illustrate the potential benefits of using computation-aided sensitizer design prior to further experimental synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Incorporating fluorinated moieties in fully conjugated donor-acceptor block copolymers

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Wang, Qing; Gomez, Enrique D.

Fully conjugated donor-acceptor block copolymers are promising candidates for photovoltaics due to their ability to microphase separate at length scales commensurate with exciton diffusion lengths. These materials can also serve as model systems to study the relationship between molecular structure, microstructure, and optoelectronic properties of conjugated polymers. The development of new donor-acceptor block copolymers relies on the manipulation of the chemical structure to fine tune properties and improve overall performance when employed in photovoltaic devices. To this end, we have demonstrated the incorporation of fluorinated moieties in conjugated block copolymers. The introduction of fluorine, a strong electron withdrawing element, is known to influence phase separation and the bandgap, and as a result, optoelectronic properties. Fluorine was introduced to the acceptor block of poly(3-hexylthiophene-2,5-diyl)-block-poly((9,9-bis(2-octyl)fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5 ',5?-diyl) (P3HT- b-PFTBT). PFTBTs were prepared with di-fluorinated and mono-fluorinated TBT. We find that fluorination impacts the bandgap, morphology and performance in devices.

Thiazole-based organic semiconductors for organic electronics.

PubMed

Lin, Yuze; Fan, Haijun; Li, Yongfang; Zhan, Xiaowei

2012-06-19

Over the past two decades, organic semiconductors have been the subject of intensive academic and commercial interests. Thiazole is a common electron-accepting heterocycle due to electron-withdrawing nitrogen of imine (C=N), several moieties based on thiazole have been widely introduced into organic semiconductors, and yielded high performance in organic electronic devices. This article reviews recent developments in the area of thiazole-based organic semiconductors, particularly thiazole, bithiazole, thiazolothiazole and benzobisthiazole-based small molecules and polymers, for applications in organic field-effect transistors, solar cells and light-emitting diodes. The remaining problems and challenges, and the key research direction in near future are discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colorless to purple-red switching electrochromic anthraquinone imides with broad visible/near-IR absorptions in the radical anion state: simulation-aided molecular design.

PubMed

Chen, Fengkun; Zhang, Jie; Jiang, Hong; Wan, Xinhua

2013-07-01

The large redshift of near-infrared (NIR) absorptions of nitro-substituted anthraquinone imide (Nitro-AQI) radical anions, relative to other AQI derivatives, is rationalized based on quantum chemical calculations. Calculations reveal that the delocalization effects of electronegative substitution in the radical anion states is dramatically enhanced, thus leading to a significant decrease in the HOMO-LUMO band gap in the radical anion states. Based on this understanding, an AQI derivative with an even stronger electron-withdrawing dicyanovinyl (di-CN) substituent was designed and prepared. The resulting molecule, di-CN-AQI, displays no absorption in the Vis/NIR region in the neutral state, but absorbs intensively in the range of λ=700-1000 (λmax ≈860 nm) and λ=1100-1800 nm (λmax ≈1400 nm) upon one-electron reduction; this is accompanied by a transition from a highly transmissive colorless solution to one that is purple-red. The relationship between calculated radical anionic HOMO-LUMO gaps and the electron-withdrawing capacity of the substituents is also determined by employing Hammett parameter, which could serve as a theoretical tool for further molecular design. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A theoretical investigation of substituent effects on the stability and reactivity of N-heterocyclic olefin carboxylates.

PubMed

Dong, Liang; Wen, Jun; Li, Weiyi

2015-08-21

A theoretical study of substituent effects on the stability and reactivity of novel synthesized N-heterocyclic olefin (NHO) carboxylates has been performed using a combination of density functional theory (DFT) calculations, molecular electrostatic potential (MESP) minimum and nucleophilicity index analyses. These calculations demonstrate that the nucleophilicity of free NHO is stronger than that of the NHO-CO2 adduct and, hence, the thermally unstable NHO-CO2 adduct should be a more efficient organocatalyst for nucleophile-mediated reactions. The stability of the NHO-CO2 adduct, as well as the reactivity of free NHO, is strongly dependent on the electronic and steric effects of the C- and N-substituents on the imidazole ring. This dependency is reflected by the measured MESP minimum for the carboxylate moiety, the NHO-CO2 adduct (Vmin1), and the terminal carbon atom of free NHO (Vmin2). C-Substituents exert only electronic effects while N-substituents exert both electronic and steric effects. In general, the electron-withdrawing groups on the C- and N-positions favor decarboxylation while weakening the reactivity of NHO. These positions favor decarboxylation due to the simultaneous decrease of the electronic density on the carboxyl moiety of the NHO-CO2 and the terminal carbon atom of olefins. Additionally, the balance between the stability of the NHO-CO2 and the reactivity of free NHO can be tuned by the combined effects of the C- and N-substituents. The introduction of weak electron-withdrawing groups at the C-position and aromatic substituents or similar ring-strained entities at the N-position favors decarboxylation of the NHO-CO2 adduct and ensures the free NHO as a strong nucleophile.

Quantitative study of interactions between oxygen lone pair and aromatic rings: substituent effect and the importance of closeness of contact.

PubMed

Gung, Benjamin W; Zou, Yan; Xu, Zhigang; Amicangelo, Jay C; Irwin, Daniel G; Ma, Shengqian; Zhou, Hong-Cai

2008-01-18

Current models describe aromatic rings as polar groups based on the fact that benzene and hexafluorobenzene are known to have large and permanent quadrupole moments. This report describes a quantitative study of the interactions between oxygen lone pair and aromatic rings. We found that even electron-rich aromatic rings and oxygen lone pairs exhibit attractive interactions. Free energies of interactions are determined using the triptycene scaffold and the equilibrium constants were determined by low-temperature 1H NMR spectroscopy. An X-ray structure analysis for one of the model compounds confirms the close proximity between the oxygen and the center of the aromatic ring. Theoretical calculations at the MP2/aug-cc-pVTZ level corroborate the experimental results. The origin of attractive interactions was explored by using aromatic rings with a wide range of substituents. The interactions between an oxygen lone pair and an aromatic ring are attractive at van der Waals' distance even with electron-donating substituents. Electron-withdrawing groups increase the strength of the attractive interactions. The results from this study can be only partly rationalized by using the current models of aromatic system. Electrostatic-based models are consistent with the fact that stronger electron-withdrawing groups lead to stronger attractions, but fail to predict or rationalize the fact that weak attractions even exist between electron-rich arenes and oxygen lone pairs. The conclusion from this study is that aromatic rings cannot be treated as a simple quadrupolar functional group at van der Waals' distance. Dispersion forces and local dipole should also be considered.

Substituent and Solvent Effects on the Absorption Spectra of Cation-π Complexes of Benzene and Borazine: A Theoretical Study.

PubMed

Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

2014-05-29

Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σ p and σ m ). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes.

Efficient approach to androstene-fused arylpyrazolines as potent antiproliferative agents. Experimental and theoretical studies of substituent effects on BF(3)-catalyzed intramolecular [3 + 2] cycloadditions of olefinic phenylhydrazones.

PubMed

Frank, Eva; Mucsi, Zoltán; Zupkó, István; Réthy, Borbála; Falkay, George; Schneider, Gyula; Wölfling, János

2009-03-25

Highly diastereoselective Lewis acid induced intramolecular 1,3-dipolar cycloadditions of alkenyl phenylhydrazones (containing various substituents on the aromatic ring) obtained from a d-secopregnene aldehyde were carried out under fairly mild conditions to furnish androst-5-ene-fused arylpyrazolines in good to excellent yields. The ability of phenylhydrazones to undergo cyclization was found to be affected significantly by the electronic features of the substituents on the aromatic moiety. The rates of the ring-closure reactions were observed to be increased by electron-donating and decreased by electron-withdrawing groups. The experimental findings on the BF(3)-catalyzed transformations were supported by calculations of the proposed mechanism at the BLYP/6-31G(d) level of theory, indicating a noteworthy dependence, mainly of the initial complexation step, and hence of the whole process, on the character of the substituent. The cycloaddition was estimated to occur via a zwitterionic intermediate rather than involving a pure concerted mechanism. The antiproliferative activities of the structurally related pyrazoline derivatives were tested in vitro on three malignant human cell lines (HeLa, MCF7, and A431): the microculture tetrazolium assay revealed that several compounds exerted marked cell growth-inhibitory effects. The highest cytotoxic activities, displayed by the p-methoxyphenylpyrazoline derivative 7d (IC(50) values: 2.01, 2.16, and 1.41 microM on HeLa, MCF7, and A341 cells, respectively), were better than those of cisplatin (IC(50) values: 12.43, 9.63, and 2.84 microM, respectively).

Designing multistep transformations using the Hammett equation: imine exchange on a copper(I) template.

PubMed

Schultz, David; Nitschke, Jonathan R

2006-08-02

Herein, we quantify how imine exchange may be used to selectively transform one metallo-organic structure into another. A series of imine exchange reactions were studied, involving a set of 4-substituted anilines, their 2-pyridylimines and 1,10-phenanthrolyl-2,9-diimines, as well as the copper complexes of these imine ligands. Electron-rich anilines were found to displace electron-poor anilines in all cases. Linear free energy relationships (LFERs) were discovered connecting the electron-donating or -withdrawing character of the 4-substituent of an aniline, as measured by the Hammett sigma(para) parameter, to that aniline's ability to compete with unsubstituted aniline to form imines. The quality of these LFERs allowed for quantitative predictions: to obtain the desired degree of selectivity in an imine exchange between anilines A and B, the required sigma(para) differential could be predicted using a variant of the Hammett equation, log(K(AB)) = rho(sigma(A) - sigma(B)). We validated this methodology by designing and executing a three-step transformation of a series of copper(I)-containing structures. Each step proceeded in predictably high yield, as calculated from sigma differentials. At each step in the series of transformations, macrocyclic structures could be created or destroyed through the selection of mono- or di-amines as subcomponents. The same methodology could be used to predict the formation of a diverse dynamic library of helicates from a set of four aniline precursors, as well as the collapse of this library into one helicate upon the addition of a fifth aniline.

The hunt for brain Aβ oligomers by peripherally circulating multi-functional nanoparticles: Potential therapeutic approach for Alzheimer disease.

PubMed

Mancini, Simona; Minniti, Stefania; Gregori, Maria; Sancini, Giulio; Cagnotto, Alfredo; Couraud, Pierre-Olivier; Ordóñez-Gutiérrez, Lara; Wandosell, Francisco; Salmona, Mario; Re, Francesca

2016-01-01

We previously showed the ability of liposomes bi-functionalized with phosphatidic acid and an ApoE-derived peptide (mApoE-PA-LIP) to reduce brain Aβ in transgenic Alzheimer mice. Herein we investigated the efficacy of mApoE-PA-LIP to withdraw Aβ peptide in different aggregation forms from the brain, using a transwell cellular model of the blood-brain barrier and APP/PS1 mice. The spontaneous efflux of Aβ oligomers (Aβo), but not of Aβ fibrils, from the 'brain' side of the transwell was strongly enhanced (5-fold) in presence of mApoE-PA-LIP in the 'blood' compartment. This effect is due to a withdrawal of Aβo exerted by peripheral mApoE-PA-LIP by sink effect, because, when present in the brain side, they did not act as Aβo carrier and limit the oligomer efflux. In vivo peripheral administration of mApoE-PA-LIP significantly increased the plasma Aβ level, suggesting that Aβ-binding particles exploiting the sink effect can be used as a therapeutic strategy for Alzheimer disease. From the Clinical Editor: Alzheimer disease (AD) at present is an incurable disease, which is thought to be caused by an accumulation of amyloid-β (Aβ) peptides in the brain. Many strategies in combating this disease have been focused on either the prevention or dissolving these peptides. In this article, the authors showed the ability of liposomes bi-functionalized with phosphatidic acid and with an ApoE- derived peptide to withdraw amyloid peptides from the brain. The data would help the future design of more novel treatment for Alzheimer disease. Copyright © 2015 Elsevier Inc. All rights reserved.

8 CFR 214.3 - Approval of schools for enrollment of F and M nonimmigrants.

Code of Federal Regulations, 2013 CFR

2013-01-01

... students and trainees, and finances (including a certified copy of the accountant's last statement of... of a denial or withdrawal. The term “in writing” means either a paper copy bearing original... in the certification as part of the site visit. Paper or electronic access is acceptable. DSOs must...

12 CFR 229.10 - Next-day availability.

Code of Federal Regulations, 2011 CFR

2011-01-01

... withdrawal not later than the business day after the banking day on which the bank received the electronic... 12 Banks and Banking 3 2011-01-01 2011-01-01 false Next-day availability. 229.10 Section 229.10 Banks and Banking FEDERAL RESERVE SYSTEM (CONTINUED) BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM...

A critical analysis of methods for rapid and nondestructive determination of wood density in standing trees

Treesearch

Shan Gao; Xiping Wang; Michael C. Wiemann; Brian K. Brashaw; Robert J. Ross; Lihai Wang

2017-01-01

Key message Field methods for rapid determination of wood density in trees have evolved from increment borer, torsiometer, Pilodyn, and nail withdrawal into sophisticated electronic tools of resistance drilling measurement. A partial resistance drilling approach coupled with knowledge of internal tree density distribution may...

TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE II SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

EPA Science Inventory

Nitrosobenzenes, the first intermediates in the reduction of nitrobenzenes, were reduced by Fe(II) solutions as well as by Fe(II)-treated goethite suspensions (Fe(II)/G). Results indicate a reactivity trend in which electron-withdrawing groups in the para position increased the ...

Synthesis and carbon-13 NMR studies of liquid crystals

NASA Astrophysics Data System (ADS)

Sun, Hong

2000-08-01

The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using 13C NMR. The method of proton encoded local field (PELF) spectroscopy was used in combination with off-magic-angle spinning (OMAS) of the sample. High-resolution 2D spectra were obtained and the order parameters were calculated from the spectra. Linear relationships between the obtained order parameters and anisotropic chemical shifts determined by 1D 13C NMR were established and semi-empirical parameters were obtained. A 1:2 mixture of 7CPB and its chain-perfluorinated analog (7PFCPB) shows interesting phase behavior with changing of temperature. The mixture was studied by the use of 13C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained by the 2D NMR method. Eight series of liquid crystals containing an electron- donating group at one end of a conjugated system and an electron-withdrawing group at the other end have been synthesized. The electron-donating group is 4- n-alkylpiperazinyl group, the electron- withdrawing group is nitro group and the conjugated system is diphenyldiazene with zero, one or two substituents on the phenyl rings. The substituents are -F, -Cl, and -CH3. Two series of compounds with cyano group as electron-withdrawing group were also synthesized. Most of the compounds synthesized are nematogenic and exhibit rather broad liquid crystalline ranges. The effects of the lateral substituents on the optical absorption and phase transition temperatures are correlated with their nature and position of substitution. Birefringence, dielectric anisotropy, elastic constant ratio and rise time of the liquid crystals were carried out using 10 wt% LC mixtures in E7. It has been found that lateral substituents have subtle effects on the properties. The presence of lateral substituents depresses melting points and clearing points of the liquid crystals. All the liquid crystals synthesized in this work have relatively large values of birefiringence, although the dielectric anisotropy values were not as high as desired. The incorporation of a fluorine atom onto the position neighboring the nitro group enhances the conjugation of the push-pull system and liquid crystals with better physical properties were obtained.

Comprehensive investigation of the excited-state dynamics of push-pull triphenylamine dyes as models for photonic applications.

PubMed

Ishow, Eléna; Clavier, Gilles; Miomandre, Fabien; Rebarz, Mateusz; Buntinx, Guy; Poizat, Olivier

2013-09-07

A series of emitting push-pull triarylamine derivatives, models of their widely used homologues in photonics and organic electronics, was investigated by steady-state and time-resolved spectroscopy. Their structural originality stems from the sole change of the electron-withdrawing substituent X (-H: 1, -CN: 2, -NO2: 3, -CHC(CN)2: 4), giving rise to efficient emission tuning from blue to red upon increasing the X electron-withdrawing character. All compounds are highly fluorescent in alkanes. The more polar compounds 2-4 undergo considerable Stokes shift and emission quenching in polar solvents. Femtosecond transient absorption data allowed us to identify the nature of the emissive state which varies as a function of the compound and surrounding polarity. A long-lived ππ* excited state with weak charge transfer character was found for 1. This excited state evolves into a long-lived ICT state with red-shifted emission for 2 in polar solvents. For 3 and 4, the ICT state is directly populated in all solvents. Long-lived and emissive in n-hexane, it relaxes in toluene to a new ICT' conformation with stronger charge transfer character and enhanced Stokes shift. In more polar THF, ethanol, and nitrile solvents, ICT relaxes to a dark excited state ICT'' with viscosity-dependent kinetics (<10 ps). The ICT'' state lifetime drops with increasing solvent polarity (150 ps for 3 in THF, 8.5 ps in butyronitrile, 1.9 ps in acetonitrile), denoting an efficient radiationless deactivation to the ground state (back charge transfer). This result reveals a very small S0-S1 energy gap at the relaxed ICT'' geometry, with a possible close-lying S0-S1 conical intersection, which suggests that the ICT → ICT'' process results from a structural change involving a large-amplitude molecular distortion. This fast structural change can account for the strong fluorescence quenching observed for 3 and 4 in polar solvents. Finally, the magnitude of intersystem crossing between the singlet and triplet excited states largely depends on the electron-deficient X unit and the solvent itself. These observations help one conclude on the prevailing role played by the electron-withdrawing groups and the surrounding polarity in the photophysical performances of triphenylamine derivatives, largely employed in numerous emissive solid-state devices.

Rumination and Cognitive Distraction in Major Depressive Disorder: An Examination of Respiratory Sinus Arrhythmia

PubMed Central

LeMoult, Joelle; Yoon, K. Lira; Joormann, Jutta

2015-01-01

Difficulty regulating emotions following stressful events is a hallmark of Major Depressive Disorder (MDD). Although individuals’ ability to regulate their emotions is believed to have direct consequences for both emotional and physical wellbeing, few studies have examined the cardiovascular effects of different emotion regulation strategies in MDD. To the best of our knowledge, the current study is the first to examine the effects of two emotion regulation strategies, cognitive distraction and rumination, on both self-reported sadness and respiratory sinus arrhythmia (RSA) in individuals with MDD and healthy controls (CTLs). Following a forced-failure stressor, participants were randomly assigned to a rumination or cognitive distraction condition. As expected, rumination increased sadness and triggered RSA withdrawal for both MDDs and CTLs. Interestingly, although cognitive distraction reduced sadness, it also triggered RSA withdrawal. Moreover, cognitive distraction was associated with greater RSA withdrawal for MDDs than CTLs. Thus, although depressed individuals are able to use cognitive distraction to emotionally recover from stress, it may be associated with greater cognitive effort. Adding low-cost physiological measures such as RSA into assessments has the potential to offer new and important information about the effects of emotion regulation on mental and physiological health. PMID:27199505

A Report of Nausea and Vomiting with Discontinuation of Chronic Use of Salvia divinorum

PubMed Central

Travis, C. R.; Ray, G. A.; Marlowe, K. F.

2012-01-01

Introduction. This is the first reported case of gastrointestinal symptoms associated with withdrawal after chronic use of this substance. Case Presentation. A 51-year-old Caucasian woman was referred to a hospital with a 3-day history of nausea, vomiting, diarrhea, and abdominal discomfort. She reported no sick family members or contact with anyone who was ill. She did report smoking 3–5 cigarettes of the herb “Salvia” consistently for 3-4 months and quit approximately 48 hours before symptoms appeared. Her use of the herb had been consistent; she smoked several cigarettes each day. Laboratory results were essentially normal including the white blood cell count. She received symptomatic treatment and was released after one day. Discussion. Salvinorin A, a kappa-opioid receptor agonist, is the major active ingredient of S. divinorum. The unique opioid properties of this herb may explain its ability to cause changes in intestinal transit time. Conclusion. A 51-year-old woman possibly developed gastrointestinal manifestations suggestive of withdrawal from Salvia divinorum after smoking the substance consistently for 3 to 4 months. The widespread use of this herb will make the potential for withdrawal syndromes more commonplace. PMID:22611407

A Report of Nausea and Vomiting with Discontinuation of Chronic Use of Salvia divinorum.

PubMed

Travis, C R; Ray, G A; Marlowe, K F

2012-01-01

Introduction. This is the first reported case of gastrointestinal symptoms associated with withdrawal after chronic use of this substance. Case Presentation. A 51-year-old Caucasian woman was referred to a hospital with a 3-day history of nausea, vomiting, diarrhea, and abdominal discomfort. She reported no sick family members or contact with anyone who was ill. She did report smoking 3-5 cigarettes of the herb "Salvia" consistently for 3-4 months and quit approximately 48 hours before symptoms appeared. Her use of the herb had been consistent; she smoked several cigarettes each day. Laboratory results were essentially normal including the white blood cell count. She received symptomatic treatment and was released after one day. Discussion. Salvinorin A, a kappa-opioid receptor agonist, is the major active ingredient of S. divinorum. The unique opioid properties of this herb may explain its ability to cause changes in intestinal transit time. Conclusion. A 51-year-old woman possibly developed gastrointestinal manifestations suggestive of withdrawal from Salvia divinorum after smoking the substance consistently for 3 to 4 months. The widespread use of this herb will make the potential for withdrawal syndromes more commonplace.

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS 2 Nanosheets via Covalent Functionalization

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

Benson, Eric E.; Zhang, Hanyu; Schuman, Samuel A.

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3CH 2) 2NPh-MoS 2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2. The p-(CHmore » 3CH 2) 2NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.« less

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS 2 Nanosheets via Covalent Functionalization

DOE PAGES

Benson, Eric E.; Zhang, Hanyu; Schuman, Samuel A.; ...

2017-12-27

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3CH 2) 2NPh-MoS 2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2. The p-(CHmore » 3CH 2) 2NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.« less

Pharmacological Treatment of Cannabis-Related Disorders: A Narrative Review.

PubMed

Gorelick, David A

2016-01-01

Cannabis is the most widely used illicit psychoactive substance world-wide, yet no medication is approved for the treatment of intoxication, withdrawal, or cannabis use disorder (CUD). To comprehensively review the current state of knowledge. Search of the PubMed electronic data base and review of reference lists of relevant articles to identify controlled clinical trials of pharmacological treatment. The search identified 4 trials for specific intoxication symptoms (none for global intoxication), 7 trials for withdrawal, and 12 phase II trials for CUD. One or two trials each suggest that propranolol is effective for some intoxication symptoms, antipsychotics for cannabis-induced psychosis, and dronabinol (synthetic THC) and gabapentin for cannabis withdrawal. Of 10 medications and one medication combination studied in 12 trials for CUD, only two medications were effective (in single trials): gabapentin and Nacetylcysteine (in adolescents). Not effective were dronabinol and several antidepressants, anticonvulsants, and antianxiety medications. Three trials of antidepressants for CUD with comorbid depression gave inconsistent results. A trial of atomoxetine for CUD with comorbid ADHD showed no efficacy. Five trials of second-generation antipsychotics for CUD with comorbid schizophrenia showed none better than any other. Further research is needed to confirm the efficacy of gabapentin for withdrawal and gabapentin and N-acetylcysteine for CUD and to develop new medications for all 3 cannabis-related disorders. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Labor market work and home care's unpaid caregivers: a systematic review of labor force participation rates, predictors of labor market withdrawal, and hours of work.

PubMed

Lilly, Meredith B; Laporte, Audrey; Coyte, Peter C

2007-12-01

As people continue to age and receive complex health care services at home, concern has arisen about the availability of family caregivers and their ability to combine employment with caregiving. This article evaluates the international research on unpaid caregivers and their labor market choices, highlighting three conclusions: first, caregivers in general are equally as likely to be in the labor force as noncaregivers; second, caregivers are more likely to work fewer hours in the labor market than noncaregivers, particularly if their caring commitments are heavy; and finally, only those heavily involved in caregiving are significantly more likely to withdraw from the labor market than noncaregivers. Policy recommendations are targeting greater access to formal care for "intensive" caregivers and developing workplace policies for employed caregivers.

Chronic intermittent ethanol induced axon and myelin degeneration is attenuated by calpain inhibition

PubMed Central

Samantaray, Supriti; Knaryan, Varduhi H.; Patel, Kaushal S.; Mulholland, Patrick J.; Becker, Howard C.; Banik, Naren L.

2015-01-01

Chronic alcohol consumption causes multifaceted damage to the central nervous system (CNS), underlying mechanisms of which are gradually being unraveled. In our previous studies, activation of calpain, a calcium-activated neutral protease has been found to cause detrimental alterations in spinal motor neurons following ethanol (EtOH) exposure in vitro. However, it is not known whether calpain plays a pivotal role in chronic EtOH exposure-induced structural damage to CNS in vivo. To test the possible involvement of calpain in EtOH-associated neurodegenerative mechanisms the present investigation was conducted in a well-established mouse model of alcohol dependence - chronic intermittent EtOH (CIE) exposure and withdrawal. Our studies indicated significant loss of axonal proteins (neurofilament light and heavy, 50-60 %), myelin proteins (myelin basic protein, 20-40 % proteolipid protein, 25 %) and enzyme (2′, 3′-cyclic-nucleotide 3′-phosphodiesterase, 21-55 %) following CIE in multiple regions of brain including hippocampus, corpus callosum, cerebellum, and importantly in spinal cord. These CIE-induced deleterious effects escalated after withdrawal in each CNS region tested. Increased expression and activity of calpain along with enhanced ratio of active calpain to calpastatin (sole endogenous inhibitor) was observed after withdrawal compared to EtOH exposure. Pharmacological inhibition of calpain with calpeptin (25 μg/kg) prior to each EtOH vapor inhalation significantly attenuated damage to axons and myelin as demonstrated by immuno-profiles of axonal and myelin proteins, and Luxol Fast Blue staining. Calpain inhibition significantly protected the ultrastructural integrity of axons and myelin compared to control as confirmed by electron microscopy. Together, these findings confirm CIE exposure and withdrawal induced structural alterations in axons and myelin, predominantly after withdrawal and corroborate calpain inhibition as a potential protective strategy against EtOH associated CNS degeneration. PMID:26100335

The efficacy of fall-risk-increasing drug (FRID) withdrawal for the prevention of falls and fall-related complications: protocol for a systematic review and meta-analysis.

PubMed

Lee, Justin Yusen; Holbrook, Anne

2017-02-20

Despite limited evidence of effectiveness, withdrawal (discontinuation or dose reduction) of high risk medications known as "fall-risk increasing drugs" (FRIDs) is typically conducted as a fall prevention strategy based on presumptive benefit. Our objective is to determine the efficacy of fall-risk increasing drugs (FRIDs) withdrawal on the prevention of falls and fall-related complications. We will search for all published and unpublished randomized controlled trials evaluating the effect of FRID withdrawal compared to usual care on the rate of falls, incidence of falls, fall-related injuries, fall-related fractures, fall-related hospitalizations, or adverse effects related to the intervention in adults aged 65 years or older. Electronic database searches will be conducted in MEDLINE, EMBASE, Cochrane Central Register of Controlled Trials (CENTRAL), and CINAHL. A grey literature search will be conducted including clinical trial registries and conference proceedings and abstracts. Two reviewers will independently perform in duplicate citation screening, full-text review, data abstraction, and risk of bias assessment. Conflicts will be resolved through team discussion or by a third reviewer if no consensus can be reached. The Grades of Recommendation, Assessment, Development and Evaluation (GRADE) criteria will be used to independently rate overall confidence in effect estimates for each outcome. Results will be synthesized descriptively, and a random effects meta-analysis will be conducted for each outcome if studies are deemed similar methodologically, clinically, and statistically. We will attempt to determine whether a FRID withdrawal strategy alone is effective at preventing falls in older adults. Our results will be used to optimize and focus fall prevention strategies and initiatives internationally with a goal of improving the health of older adults. PROSPERO CRD42016040203.

Regioselective copper-catalyzed N(1)-(hetero)arylation of protected histidine.

PubMed

Sharma, Krishna K; Mandloi, Meenakshi; Jain, Rahul

2016-09-26

We report regioselective N(1)-arylation of protected histidine using copper(i) iodide as a catalyst, trans-N,N'-dimethylcyclohexane-1,2-diamine as a ligand and readily available aryl iodides as coupling partners under microwave irradiation at 130 °C for 40 min. The reaction provides rapid access to electron-donating, electron-withdrawing and bulky group substituted N-arylated histidines in high yields, including previously inaccessible N-heteroaryl histidines. These N(1)-(hetero)aryl histidines are promising building blocks in peptide-based drug design and discovery.

Emission color tuning in AlQ3 complexes with extended conjugated chromophores.

PubMed

Pohl, Radek; Anzenbacher, Pavel

2003-08-07

[reaction: see text] A new method for the synthesis of 5-arylethynyl-8-hydroxyquinoline ligands using Sonogashira-Hagihara coupling was developed. The electronic nature of arylethynyl substituents affects the emission color and quantum yield of the resulting Al(III) complex. Photophysical properties of the metallocomplexes correspond to the electron-withdrawing/-donating character of the arylethynyl substituents. Optical properties of such Al(III) complexes correlate with the Hammett constant values of the respective substituents. This strategy offers a powerful tool for the preparation of electroluminophores with predictable photophysical properties.

New Stable Cu(I) Catalyst Supported on Weakly Acidic Polyacrylate Resin for Green C-N Coupling: Synthesis of N-(Pyridin-4-yl)benzene Amines and N,N-Bis(pyridine-4-yl)benzene Amines.

PubMed

Kore, Nitin; Pazdera, Pavel

2016-12-22

A method for preparation of a new stable Cu(I) catalyst supported on weakly acidic polyacrylate resin without additional stabilizing ligands is described. A simple and efficient methodology for Ullmann Cu(I) catalyzed C-N cross coupling reactions using this original catalyst is reported. Coupling reactions of 4-chloropyridinium chloride with anilines containing electron donating (EDG) or electron withdrawing (EWG) groups, naphthalen-2-amine and piperazine, respectively, are successfully demonstrated.

Effects of Using an Ipod App to Manage Recreation Tasks

ERIC Educational Resources Information Center

Uphold, Nicole M.; Douglas, Karen H.; Loseke, Dannell L.

2016-01-01

A withdrawal design study evaluated the effectiveness of using constant time delay to teach six adults with a developmental disability to program and use an iPod touch® as an electronic photographic activity schedule (ePAS). The ePAS, created with the First Then Visual Schedule app, consisted of photographs of different exercises to complete…

17 CFR 275.203-2 - Withdrawal from investment adviser registration.

Code of Federal Regulations, 2010 CFR

2010-04-01

... application). (b) Electronic filing. Once you have filed your Form ADV (17 CFR 279.1) (or any amendments to... file must be filed with the IARD, unless you have received a hardship exemption under § 275.203-3. (c... EXCHANGE COMMISSION (CONTINUED) RULES AND REGULATIONS, INVESTMENT ADVISERS ACT OF 1940 § 275.203-2...

31 CFR 363.42 - How will my interest income be reported for tax purposes?

Code of Federal Regulations, 2010 CFR

2010-07-01

... TreasuryDirect § 363.42 How will my interest income be reported for tax purposes? When you open your TreasuryDirect ® account, you consent to receive the appropriate tax reporting forms by electronic means... printable form through your TreasuryDirect account. If you withdraw your consent to receive tax reporting...

Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings

PubMed Central

Zahran, Zaki N.; Mohamed, Eman A.; Naruta, Yoshinori

2016-01-01

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe−containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push−pull mechanism. Bio−inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe−Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe−Fe separation distance. PMID:27087483

Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings.

PubMed

Zahran, Zaki N; Mohamed, Eman A; Naruta, Yoshinori

2016-04-18

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance.

Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings

NASA Astrophysics Data System (ADS)

Zahran, Zaki N.; Mohamed, Eman A.; Naruta, Yoshinori

2016-04-01

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance.

Labor Market Work and Home Care's Unpaid Caregivers: A Systematic Review of Labor Force Participation Rates, Predictors of Labor Market Withdrawal, and Hours of Work

PubMed Central

Lilly, Meredith B; Laporte, Audrey; Coyte, Peter C

2007-01-01

As people continue to age and receive complex health care services at home, concern has arisen about the availability of family caregivers and their ability to combine employment with caregiving. This article evaluates the international research on unpaid caregivers and their labor market choices, highlighting three conclusions: first, caregivers in general are equally as likely to be in the labor force as noncaregivers; second, caregivers are more likely to work fewer hours in the labor market than noncaregivers, particularly if their caring commitments are heavy; and finally, only those heavily involved in caregiving are significantly more likely to withdraw from the labor market than noncaregivers. Policy recommendations are targeting greater access to formal care for “intensive” caregivers and developing workplace policies for employed caregivers. PMID:18070333

Proneurotrophin-3 promotes cell cycle withdrawal of developing cerebellar granule cell progenitors via the p75 neurotrophin receptor.

PubMed

Zanin, Juan Pablo; Abercrombie, Elizabeth; Friedman, Wilma J

2016-07-19

Cerebellar granule cell progenitors (GCP) proliferate extensively in the external granule layer (EGL) of the developing cerebellum prior to differentiating and migrating. Mechanisms that regulate the appropriate timing of cell cycle withdrawal of these neuronal progenitors during brain development are not well defined. The p75 neurotrophin receptor (p75(NTR)) is highly expressed in the proliferating GCPs, but is downregulated once the cells leave the cell cycle. This receptor has primarily been characterized as a death receptor for its ability to induce neuronal apoptosis following injury. Here we demonstrate a novel function for p75(NTR) in regulating proper cell cycle exit of neuronal progenitors in the developing rat and mouse EGL, which is stimulated by proNT3. In the absence of p75(NTR), GCPs continue to proliferate beyond their normal period, resulting in a larger cerebellum that persists into adulthood, with consequent motor deficits.

Iron Supplementation Associated With Loss of Phenotype in Autosomal Dominant Hypophosphatemic Rickets.

PubMed

Kapelari, Klaus; Köhle, Julia; Kotzot, Dieter; Högler, Wolfgang

2015-09-01

Autosomal dominant hypophosphatemic rickets (ADHR) is the only hereditary disorder of renal phosphate wasting in which patients may regain the ability to conserve phosphate. Low iron status plays a role in the pathophysiology of ADHR. This study reports of a girl with ADHR, iron deficiency, and a paternal history of hypophosphatemic rickets that resolved without treatment. The girl's biochemical phenotype resolved with iron supplementation. A 26-month-old girl presented with typical features of hypophosphatemic rickets, short stature (79 cm; -2.82 SDS), and iron deficiency. Treatment with elemental phosphorus and calcitriol improved her biochemical profile and resolved the rickets. The girl's father had presented with rickets at age 11 months but never received medication. His final height was reduced (154.3 cm; -3.51 SDS), he had undergone corrective leg surgery and had an adult normal phosphate, fibroblast growth factor 23, and iron status. Father and daughter were found to have a heterozygous mutation in exon 3 of the FGF23 gene (c.536G>A, p.Arg179Gln), confirming ADHR. Withdrawal of rickets medication was attempted off and on iron supplementation. Withdrawal of rickets medication in the girl was unsuccessful in the presence of low-normal serum iron levels at age 5.6 years but was later successful in the presence of high-normal serum iron levels following high-dose iron supplementation. We report an association between iron supplementation and a complete loss of biochemical ADHR phenotype, allowing withdrawal of rickets medication. Experience from this case suggests that reduction and withdrawal of rickets medication should be attempted only after iron status has been optimized.

The dose effects of short-term dronabinol (oral THC) maintenance in daily cannabis users.

PubMed

Vandrey, Ryan; Stitzer, Maxine L; Mintzer, Miriam Z; Huestis, Marilyn A; Murray, Jeannie A; Lee, Dayong

2013-02-01

Prior studies have separately examined the effects of dronabinol (oral THC) on cannabis withdrawal, cognitive performance, and the acute effects of smoked cannabis. A single study examining these clinically relevant domains would benefit the continued evaluation of dronabinol as a potential medication for the treatment of cannabis use disorders. Thirteen daily cannabis smokers completed a within-subject crossover study and received 0, 30, 60 and 120mg dronabinol per day for 5 consecutive days. Vital signs and subjective ratings of cannabis withdrawal, craving and sleep were obtained daily; outcomes under active dose conditions were compared to those obtained under placebo dosing. On the 5th day of medication maintenance, participants completed a comprehensive cognitive performance battery and then smoked five puffs of cannabis for subjective effects evaluation. Each dronabinol maintenance period occurred in a counterbalanced order and was separated by 9 days of ad libitum cannabis use. Dronabinol dose-dependently attenuated cannabis withdrawal and resulted in few adverse side effects or decrements in cognitive performance. Surprisingly, dronabinol did not alter the subjective effects of smoked cannabis, but cannabis-induced increases in heart rate were attenuated by the 60 and 120mg doses. Dronabinol's ability to dose-dependently suppress cannabis withdrawal may be therapeutically beneficial to individuals trying to stop cannabis use. The absence of gross cognitive impairment or side effects in this study supports safety of doses up to 120mg/day. Continued evaluation of dronabinol in targeted clinical studies of cannabis treatment, using an expanded range of doses, is warranted. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

The Dose Effects of Short-Term Dronabinol (Oral THC) Maintenance in Daily Cannabis Users

PubMed Central

Vandrey, Ryan; Stitzer, Maxine L.; Mintzer, Miriam Z.; Huestis, Marilyn A.; Murray, Jeannie A.; Lee, Dayong

2012-01-01

BACKGROUND Prior studies have separately examined the effects of dronabinol (oral THC) on cannabis withdrawal, cognitive performance, and the acute effects of smoked cannabis. A single study examining these clinically relevant domains would benefit the continued evaluation of dronabinol as a potential medication for the treatment of cannabis use disorders. METHODS Thirteen daily cannabis smokers completed a within-subject crossover study and received 0, 30, 60 and 120 mg dronabinol per day for 5 consecutive days. Vital signs and subjective ratings of cannabis withdrawal, craving and sleep were obtained daily; outcomes under active dose conditions were compared to those obtained under placebo dosing. On the 5th day of medication maintenance, participants completed a comprehensive cognitive performance battery and then smoked 5 puffs of cannabis for subjective effects evaluation. Each dronabinol maintenance period occurred in a counterbalanced order and was separated by 9 days of ad-libitum cannabis use. RESULTS Dronabinol dose-dependently attenuated cannabis withdrawal and resulted in few adverse side effects or decrements in cognitive performance. Surprisingly, dronabinol did not alter the subjective effects of smoked cannabis, but cannabis-induced increases in heart rate were attenuated by the 60 and 120 mg doses. CONCLUSIONS Dronabinol’s ability to dose-dependently suppress cannabis withdrawal may be therapeutically beneficial to individuals trying to stop cannabis use. The absence of gross cognitive impairment or side effects in this study supports safety of doses up to 120mg per day. Continued evaluation of dronabinol in targeted clinical studies of cannabis treatment, using an expanded range of doses, is warranted. PMID:22921474

The emerging phenomenon of electronic cigarettes.

PubMed

Caponnetto, Pasquale; Campagna, Davide; Papale, Gabriella; Russo, Cristina; Polosa, Riccardo

2012-02-01

The need for novel and more effective approaches to tobacco control is unquestionable. The electronic cigarette is a battery-powered electronic nicotine delivery system that looks very similar to a conventional cigarette and is capable of emulating smoking, but without the combustion products accountable for smoking's damaging effects. Smokers who decide to switch to electronic cigarettes instead of continuing to smoke would achieve large health gains. The electronic cigarette is an emerging phenomenon that is becoming increasingly popular with smokers worldwide. Users report buying them to help quit smoking, to reduce cigarette consumption, to relieve tobacco withdrawal symptoms due to workplace smoking restrictions and to continue to have a 'smoking' experience but with reduced health risks. The focus of the present article is the health effects of using electronic cigarettes, with consideration given to the acceptability, safety and effectiveness of this product to serve as a long-term substitute for smoking or as a tool for smoking cessation.

Mu-opioid receptor redistribution in the locus coeruleus upon precipitation of withdrawal in opiate-dependent rats.

PubMed

Scavone, Jillian L; Van Bockstaele, Elisabeth J

2009-03-01

Administration of mu-opioid receptor (MOR) agonists is known to produce adaptive changes within noradrenergic neurons of the rat locus coeruleus (LC). Alterations in the subcellular distribution of MOR have been shown to occur in the LC in response to full agonists and endogenous peptides; however, there is considerable debate in the literature whether trafficking of MOR occurs after chronic exposure to the partial-agonist morphine. In the present study, we examined adaptations in MOR after chronic opioid exposure using immunofluorescence and electron microscopy (EM), using receptor internalization as a functional endpoint. MOR trafficking in LC neurons was characterized in morphine-dependent rats that were given naltrexone at a dose known to precipitate withdrawal. After chronic morphine exposure, a subtle redistribution of MOR immunoreactivity from the membrane to the cytosol was detected within dendrites of LC neurons. Interestingly, an acute injection of naltrexone in rats exposed to chronic morphine produced a robust internalization of MOR, whereas administration of naltrexone failed to do so in naïve animals. These findings provide anatomical evidence for modified regulation of MOR trafficking after chronic morphine treatment in brain noradrenergic neurons. Adaptations in the MOR signaling pathways that regulate internalization may occur as a consequence of chronic treatment and precipitation of withdrawal. Mechanisms underlying this effect might include differential MOR regulation in the LC, or downstream effects of withdrawal-induced enkephalin (ENK) release from afferents to the LC. (c) 2009 Wiley-Liss, Inc.

PULSED ION SOURCE

DOEpatents

Martina, E.F.

1958-10-14

An improved pulsed ion source of the type where the gas to be ionized is released within the source by momentary heating of an electrode occluded with the gas is presented. The other details of the ion source construction include an electron emitting filament and a positive reference grid, between which an electron discharge is set up, and electrode means for withdrawing the ions from the source. Due to the location of the gas source behind the electrode discharge region, and the positioning of the vacuum exhaust system on the opposite side of the discharge, the released gas is drawn into the electron discharge and ionized in accurately controlled amounts. Consequently, the output pulses of the ion source may be accurately controlled.

Conversion and origin of normal and abnormal temperature dependences of kinetic isotope effect in hydride transfer reactions.

PubMed

Zhu, Xiao-Qing; Li, Xiu-Tao; Han, Su-Hui; Mei, Lian-Rui

2012-05-18

The effects of substituents on the temperature dependences of kinetic isotope effect (KIE) for the reactions of the hydride transfer from the substituted 5-methyl-6-phenyl-5,6-dihydrophenanthridine (G-PDH) to thioxanthylium (TX(+)) in acetonitrile were examined, and the results show that the temperature dependences of KIE for the hydride transfer reactions can be converted by adjusting the nature of the substituents in the molecule of the hydride donor. In general, electron-withdrawing groups can make the KIE to have normal temperature dependence, but electron-donating groups can make the KIE to have abnormal temperature dependence. Thermodynamic analysis on the possible pathways of the hydride transfer from G-PDH to TX(+) in acetonitrile suggests that the transfers of the hydride anion in the reactions are all carried out by the concerted one-step mechanism whether the substituent is an electron-withdrawing group or an electron-donating group. But the examination of Hammett-type free energy analysis on the hydride transfer reactions supports that the concerted one-step hydride transfer is not due to an elementary chemical reaction. The experimental values of KIE at different temperatures for the hydride transfer reactions were modeled by using a kinetic equation formed according to a multistage mechanism of the hydride transfer including a returnable charge-transfer complex as the reaction intermediate; the real mechanism of the hydride transfer and the root that why the temperature dependences of KIE can be converted as the nature of the substituents are changed were discovered.

Effects of shape, size, and pyrene doping on electronic properties of graphene nanoflakes.

PubMed

Kuamit, Thanawit; Ratanasak, Manussada; Rungnim, Chompoonut; Parasuk, Vudhichai

2017-11-25

Effects of size, shape, and pyrene doping on electronic properties of graphene nanoflakes (GNFs) were theoretically investigated using density functional theory method with PBE, B3PW91, and M06-2X functionals and cc-pVDZ basis set. Two shapes of zigzag GNFs, hexagonal (HGN) and rhomboidal (RGN), were considered. The energy band gap of GNF depends on shape and decreases with size. The HGN has larger band gap energy (1.23-3.96 eV) than the RGN (0.13-2.12 eV). The doping of pyrene and pyrene derivatives on both HGN and RGN was also studied. The adsorption energy of pyrene and pyrene derivatives on GNF does not depend on the shape of GNFs with energies between 21 and 27 kcal mol -1 . The substituent on pyrene enhances the binding to GNF but the strength does not depend on electron withdrawing or donating capability. The doping by pyrene and pyrene derivatives also shifts the HOMO and LUMO energies of GNFs. Both positive (destabilizing) and negative (stabilizing) shifts on HOMO and LUMO of GNFs were seen. The direction and magnitude of the shift do not follow the electron withdrawing and donating capability of pyrene substituents. However, only a slight shift was observed for doped RGN. A shift of 0.19 eV was noticed for HOMO of HGN doped with 1-aminopyrene (pyNH 2 ) and of 0.04 eV for LUMO of HGN doped with 1-pyrenecarboxylic acid (pyCOOH). Graphical Abstract HOMO and LUMO Energies of pyrene/pyrene derivatives doped Graphene Nanoflakes.

Rubrolides as model for the development of new lactones and their aza analogs as potential photosynthesis inhibitors.

PubMed

Pereira, Ulisses A; Barbosa, Luiz C A; Demuner, Antônio J; Silva, Antônio A; Bertazzini, Michele; Forlani, Giuseppe

2015-07-01

Natural phytotoxins and their synthetic analogs are a potential source of new bioactive compounds for agriculture. Analogs of rubrolides, a class of γ-alkylidene-γ-lactones isolated from different ascidians, have been shown to interfere with the photosynthetic electron-transport chain, yet their activity needs to be improved. With this aim, ten 5-aryl-6-benzyl-4-bromopyridazin-3(2H)-ones were prepared in yields ranging from 44 to 88% by reaction of their correspondent γ-alkylidene-γ-lactones with NH2 NH2 . The structures of these rubrolide analogs were determined by (1) H- and (13) C-NMR, 2D-NMR (COSY and HETCOR), NOE difference, and MS techniques. These compounds were evaluated for their abilities of interfering with the light-driven reduction of ferricyanide by isolated spinach chloroplasts. Lactones with electron-withdrawing substituents in the para-position of the benzylidene ring were the most effective inhibitors. Characterization of the activity of 11b/11b' suggested a mechanism based on the interaction with the plastoquinone binding site of photosystem II. Addition of several compounds to the culture medium of a cyanobacterial model strain was found to inhibit algal growth. However, the relative effectiveness was not consistent with their activity in vitro, suggesting the occurrence of multiple targets and/or detoxyfication mechanisms. Indeed, the compounds showed differential effects on the heterotrophic growth of some crop species, Cucumis sativus and Sorghum bicolor. Pyridazin-3(2H)-ones 12e, 12i, and 12j, which have been found poorly active against the photosynthetic electron transport, were the most effective in inhibiting the growth of some weeds, Ipomoea grandifolia and Brachiaria decumbens, under greenhouse conditions. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

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

A test of the opponent-process theory of motivation using lesions that selectively block morphine reward.

PubMed

Vargas-Perez, Hector; Ting-A-Kee, Ryan A; Heinmiller, Andrew; Sturgess, Jessica E; van der Kooy, Derek

2007-06-01

The opponent-process theory of motivation postulates that motivational stimuli activate a rewarding process that is followed by an opposed aversive process in a homeostatic control mechanism. Thus, an acute injection of morphine in nondependent animals should evoke an acute rewarding response, followed by a later aversive response. Indeed, the tegmental pedunculopontine nucleus (TPP) mediates the rewarding effects of opiates in previously morphine-naive animals, but not other unconditioned effects of opiates, or learning ability. The aversive opponent process for acute morphine reward was revealed using a place-conditioning paradigm. The conditioned place aversion induced by 16-h spontaneous morphine withdrawal from an acute morphine injection in nondependent rats was abolished by TPP lesions performed prior to drug experience. However, TPP-lesioned rats did show conditioned aversions for an environment paired with the acute administration of the opioid antagonist naloxone, which blocks endogenous opioids. The results show that blocking the rewarding effects of morphine with TPP lesions also blocked the opponent aversive effects of acute morphine withdrawal in nondependent animals. Thus, this spontaneous withdrawal aversion (the opponent process) is induced by the acute rewarding effects of morphine and not by other unconditioned effects of morphine, the pharmacological effects of morphine or endogenous opioids being displaced from opiate receptors.

A Monte Carlo Analysis of Weight Data from UF 6 Cylinder Feed and Withdrawal Stations

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

Garner, James R; Whitaker, J Michael

2015-01-01

As the number of nuclear facilities handling uranium hexafluoride (UF 6) cylinders (e.g., UF 6 production, enrichment, and fuel fabrication) increase in number and throughput, more automated safeguards measures will likely be needed to enable the International Atomic Energy Agency (IAEA) to achieve its safeguards objectives in a fiscally constrained environment. Monitoring the process data from the load cells built into the cylinder feed and withdrawal (F/W) stations (i.e., cylinder weight data) can significantly increase the IAEA’s ability to efficiently achieve the fundamental safeguards task of confirming operations as declared (i.e., no undeclared activities). Researchers at the Oak Ridge Nationalmore » Laboratory, Los Alamos National Laboratory, the Joint Research Center (in Ispra, Italy), and University of Glasgow are investigating how this weight data can be used for IAEA safeguards purposes while fully protecting the operator’s proprietary and sensitive information related to operations. A key question that must be resolved is, what is the necessary frequency of recording data from the process F/W stations to achieve safeguards objectives? This paper summarizes Monte Carlo simulations of typical feed, product, and tails withdrawal cycles and evaluates longer sampling frequencies to determine the expected errors caused by low-frequency sampling and its impact on material balance calculations.« less

76 FR 28426 - Withdrawal of Notice Inviting Applications for New Awards for Fiscal Year (FY) 2011...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-17

... the FRS, toll free, at 1--800--877--8339. Electronic Access to This Document: The official version of this document is the document published in the Federal Register. Free Internet access to the official... or by e-mail: [email protected] . If you use a TDD, call the Federal Relay Service (FRS), toll free...

The synthesis of 5-substituted ring E analogs of methyllycaconitine via the Suzuki-Miyaura cross-coupling reaction.

PubMed

Huang, Junfeng; Orac, Crina M; McKay, Susan; McKay, Dennis B; Bergmeier, Stephen C

2008-04-01

Novel 3,5-disubstituted ring E analogs of methyllycaconitine were prepared and evaluated in nicotinic acetylcholine receptor binding assays. The desired analogs were prepared through the Suzuki-Miyaura cross-coupling reaction of methyl 5-bromo-nicotinate. The Suzuki-Miyaura cross-coupling reactions of pyridines with electron withdrawing substituents have not been extensively described previously.

Synthesis and characterization of an Fe(i) cage complex with high stability towards strong H-acids.

PubMed

Voloshin, Yan Z; Novikov, Valentin V; Nelyubina, Yulia V; Belov, Alexander S; Roitershtein, Dmitrii M; Savitsky, Anton; Mokhir, Andriy; Sutter, Jörg; Miehlich, Matthias E; Meyer, Karsten

2018-04-03

The first synthesized and X-ray structurally characterized "classical" iron(i) dioximate showed an unrivaled stability towards strong acids, thus calling for a reassessment of the origins of the electrocatalytic activity of similar low-valent cobalt and iron cage complexes with electron-withdrawing ribbed substituents, shown previously to be effective electrocatalysts of the HER.

Dual Functioning Thieno-Pyrrole Fused BODIPY Dyes for NIR Optical Imaging and Photodynamic Therapy: Singlet Oxygen Generation without Heavy Halogen Atom Assistance.

PubMed

Watley, Ryan L; Awuah, Samuel G; Bio, Moses; Cantu, Robert; Gobeze, Habtom B; Nesterov, Vladimir N; Das, Sushanta K; D'Souza, Francis; You, Youngjae

2015-06-01

We discovered a rare phenomenon wherein a thieno-pyrrole fused BODIPY dye (SBDPiR690) generates singlet oxygen without heavy halogen atom substituents. SBDPiR690 generates both singlet oxygen and fluorescence. To our knowledge, this is the first example of such a finding. To establish a structure-photophysical property relationship, we prepared SBDPiR analogs with electron-withdrawing groups at the para-position of the phenyl groups. The electron-withdrawing groups increased the HOMO-LUMO energy gap and singlet oxygen generation. Among the analogs, SBDPiR688, a CF3 analog, had an excellent dual functionality of brightness (82290 m(-1)  cm(-1) ) and phototoxic power (99170 m(-1)  cm(-1) ) comparable to those of Pc 4, due to a high extinction coefficient (211 000 m(-1)  cm(-1) ) and balanced decay (Φflu =0.39 and ΦΔ =0.47). The dual functionality of the lead compound SBDPiR690 was successfully applied to preclinical optical imaging and for PDT to effectively control a subcutaneous tumor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interactions of p-Nitrobenzene Diazonium Fluoroborate and Analogs with the Active Sites of Acetylcholine-Receptor and -Esterase*

PubMed Central

Mautner, Henry G.; Bartels, Eva

1970-01-01

p-Nitrobenzene diazonium fluoroborate (NDF) is a potent inhibitor of the carbamylcholine-induced depolarization of the electroplax and of acetylcholinesterase. It probably forms covalent bonds with the acetylcholine-receptor and -esterase at the active site of the proteins. Its inhibitory strength is at least the same as that of trimethylammonium diazonium fluoroborate (TDF). The p-acetoxy analog, with its weaker electron-withdrawing group, is about ten times weaker as an inhibitor than the trimethylammonium or p-nitro analogs, both of which have strong electron-withdrawing groups. After treatment of the electroplax preparation with dithiothreitol, NDF remains an irreversible receptor-inhibitor, while TDF becomes a potent reversible receptor-activator. TDF is self-inhibitory: applied before reduction, it no longer depolarizes. Although the first observations on TDF suggested that the compound labels both proteins by virtue of the steric complementary of its trimethylammonium group to a negative subsite in the proteins, the present study indicates that it is the positively charged diazonium group that reacts with the active sites of the proteins to form a covalent bond with an appropriate amino-acid residue. PMID:5272331

Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

PubMed

Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

2011-03-17

The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

An organoboron compound with a wide absorption spectrum for solar cell applications.

PubMed

Liu, Fangbin; Ding, Zicheng; Liu, Jun; Wang, Lixiang

2017-11-09

Organoboron compounds offer new approaches to tune the electronic structures of π-conjugated molecules. In this work, an electron acceptor (M-BNBP4P-1) is developed by endcapping an organoboron core unit with two strong electron-withdrawing groups. M-BNBP4P-1 exhibits a unique wide absorption spectrum with two strong absorption bands in the long wavelength region (λ max = 771 nm) and the short wavelength region (λ max = 502 nm), which indicate superior sunlight harvesting capability. This is due to its special electronic structure, i.e. a delocalized LUMO and a localized HOMO. Prototype solution-processed organic solar cells based on M-BNBP4P-1 show a power conversion efficiency of 7.06% and a wide photoresponse from 350 nm to 880 nm.

29 CFR 4219.11 - Withdrawal liability upon mass withdrawal.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 9 2010-07-01 2010-07-01 false Withdrawal liability upon mass withdrawal. 4219.11 Section... Redetermination of Withdrawal Liability Upon Mass Withdrawal § 4219.11 Withdrawal liability upon mass withdrawal. (a) Initial withdrawal liability. The plan sponsor of a multiemployer plan that experiences a mass...

29 CFR 4219.11 - Withdrawal liability upon mass withdrawal.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 9 2011-07-01 2011-07-01 false Withdrawal liability upon mass withdrawal. 4219.11 Section... Redetermination of Withdrawal Liability Upon Mass Withdrawal § 4219.11 Withdrawal liability upon mass withdrawal. (a) Initial withdrawal liability. The plan sponsor of a multiemployer plan that experiences a mass...

Persistence of blood changes associated with alteration of the dietary electrolyte balance in commercial pigs after feed withdrawal, transportation, and lairage, and the effects on performance and carcass quality.

PubMed

Edwards, L N; Engle, T E; Paradis, M A; Correa, J A; Anderson, D B

2010-12-01

Increasing dietary electrolyte balance (dEB) has previously been shown to reduce the incidence of nonambulatory and noninjured swine, improve meat quality, and reduce the incidence of gastric ulcers. The objective of this study was to evaluate the effect of dEB under commercial conditions. Due to the variability in feed withdrawal, transport, and lairage conditions in the swine industry, it was necessary to determine first the persistence of blood changes during the marketing process after alteration of dEB. Sixteen pens of 8 crossbred barrows were assigned to a low (121 mEq/kg) or high (375 mEq/kg) dEB diet, calculated as Na(+) + K(+) - Cl(-), to determine the persistence of blood changes associated with the alteration of dEB. Diets were formulated to meet or exceed NRC (1998) requirements for energy, protein, vitamins, and minerals. Dietary treatments were provided for ad libitum intake for 3 d before slaughter. Before transport, animals were fasted in the barn for approximately 10 h. After fasting, animals were shipped to the packing plant, rested for 8 h, and subsequently slaughtered. Initial and final BW of the animals were obtained. Blood was sampled at baseline (2 d before administration of diets), before feed withdrawal (0 h), after feed withdrawal (10 h), and at exsanguination (20 h). Consumption of the high dEB diet for 3 d resulted in an increase in blood TCO(2) (P = 0.001), HCO(3)(-) (P = 0.001), and base excess (P = 0.0003) and a decrease in Cl(-) (P = 0.0002) and anion gap (P = 0.01). These differences, however, were not maintained for any of the blood components after the 10-h feed withdrawal (P > 0.22). Increasing dEB had no adverse effects (P > 0.18) on growth performance, meat quality, or carcass yield and did not decrease pars esophageal ulcer scores. This study demonstrated that the effect of dEB on blood components was not maintained after a 10-h feed withdrawal. Therefore, it is likely that the ability of the animal to withstand any increased metabolic acid load associated with the stress of transport was lost after feed withdrawal. Further research is needed to determine the effects of dEB alteration in animals that have not been fasted before shipment and using diets with a larger difference in dEB.

The Influence of the Anionic Counter-Ion on the Activity of Ammonium Substituted Hoveyda-Type Olefin Metathesis Catalysts in Aqueous Media

NASA Astrophysics Data System (ADS)

Gułajski, Łukasz; Grela, Karol

Polar olefin metathesis catalysts, bearing an ammonium group are presented. The electron withdrawing ammonium group not only activates the catalysts electronically, but at the same time makes the catalysts more hydrophilic. Catalysts can be therefore efficiently used not only in traditional media, such as methylene chloride and toluene, but also in technical-grade alcohols, alcohol— water mixtures and in neat water. Finally, in this overview the influence of the anionic counter-ion on the activity of ammonium substituted Hoveyda-type olefin metathesis catalysts in aqueous media is presented.

Effects of the capping ligands, linkers and oxide surface on the electron injection mechanism of copper sulfide quantum dot-sensitized solar cells.

PubMed

Suárez, Javier Amaya; Plata, Jose J; Márquez, Antonio M; Sanz, Javier Fdez

2017-06-07

Quantum dot-sensitized solar cells, QDSCs, are a clean and effective alternative to fossil fuels to reduce CO 2 emissions. However, the different components that constitute the QDSCs and the difficulty of isolating experimentally their effects on the performance of the whole system slow down the development of more efficient devices. In this work, DFT calculations are combined with a bottom-up approach to differentiate the effect of each component on the electronic structure and absorption spectra. First, Cu 2 S QDs were built including a U parameter to effectively describe the localization of electrons. The effect of capping agents is addressed using ligands with different electron-donating/withdrawing groups. The role of linkers and their adsorption on the oxide surface are also examined. Finally, we propose a main indirect electron injection mechanism based on the position of the peaks of the spectra.

Investigation of phase transition properties of ZrO2 thin films

NASA Astrophysics Data System (ADS)

Kumar, Davinder; Singh, Avtar; Kaur, Manpreet; Rana, Vikrant Singh; Kaur, Raminder

2018-05-01

This paper presents the synthesis of transparent thin films of zirconium oxide (ZrO2) deposited on glass substrates by sol-gel dip coating technique. Synthesized films were characterized for different annealing time and withdrawal speed. Change in crystallographic properties of thin films was investigated by using X-ray diffraction. Surface morphology of transparent thin films was estimated by using scanning electron microscope.

Computationally designed and experimentally confirmed diastereoselective rhodium-catalyzed Pauson-Khand reaction at room temperature.

PubMed

Baik, Mu-Hyun; Mazumder, Shivnath; Ricci, Paolo; Sawyer, James R; Song, Ye-Geun; Wang, Huijun; Evans, P Andrew

2011-05-25

The computational analysis of the rhodium-catalyzed Pauson-Khand reaction indicates that the key transition state is highly charge-polarized, wherein different diastereoisomers have distinctively different charge polarization patterns. Experimental studies demonstrate that chloro-enynes provide the optimal σ-electron-withdrawing group to promote polarization and thereby reduce the activation barrier to provide a highly diastereoselective reaction at room temperature.

Mild and efficient molybdenum-mediated Pauson-Khand-type reaction.

PubMed

Adrio, Javier; Rivero, Marta Rodríguez; Carretero, Juan Carlos

2005-02-03

[reaction: see text] The molybdenum-mediated Pauson-Khand reaction promoted by Mo(CO)3(DMF)3 takes place under very mild conditions in the absence of any promoter. High yields in Pauson-Khand adducts are obtained in the cyclization of a wide variety of functionalized 1,6- and 1,7-enynes. Enynes bearing electron withdrawing groups at the alkene terminus are particularly good substrates.

Tracking bacterial infection of macrophages using a novel red-emission pH sensor.

PubMed

Jin, Yuguang; Tian, Yanqing; Zhang, Weiwen; Jang, Sei-Hum; Jen, Alex K-Y; Meldrum, Deirdre R

2010-10-01

The relationship between bacteria and host phagocytic cells is key to the induction of immunity. To visualize and monitor bacterial infection, we developed a novel bacterial membrane permeable pH sensor for the noninvasive monitoring of bacterial entry into murine macrophages. The pH sensor was constructed using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) as an electron-withdrawing group and aniline as an electron-donating group. A piperazine moiety was used as the pH-sensitive group. Because of the strong electron-donating and -withdrawing units conjugated in the sensing moiety M, the fluorophore emitted in the red spectral window, away from the autofluorescence regions of the bacteria. Following the engulfment of sensor-labeled bacteria by macrophages and their subsequent merger with host lysosomes, the resulting low-pH environment enhances the fluorescence intensity of the pH sensors inside the bacteria. Time-lapse analysis of the fluorescent intensity suggested significant heterogeneity of bacterial uptake among macrophages. In addition, qRT-PCR analysis of the bacterial 16 S rRNA gene expression within single macrophage cells suggested that the 16 S rRNA of the bacteria was still intact 120 min after they had been engulfed by macrophages. A toxicity assay showed that the pH sensor has no cytotoxicity towards either E. coli or murine macrophages. The sensor shows good repeatability, a long lifetime, and a fast response to pH changes, and can be used for a variety of bacteria.

A modification of the Hammett equation for predicting ionisation constants of p-vinyl phenols.

PubMed

Sipilä, Julius; Nurmi, Harri; Kaukonen, Ann Marie; Hirvonen, Jouni; Taskinen, Jyrki; Yli-Kauhaluoma, Jari

2005-01-01

Currently there are several compounds used as drugs or studied as new chemical entities, which have an electron withdrawing group connected to a vinylic double bond in a phenolic or catecholic core structure. These compounds share a common feature--current computational methods utilizing the Hammett type equation for the prediction of ionisation constants fail to give accurate prediction of pK(a)'s for compounds containing the vinylic moiety. The hypothesis was that the effect of electron-withdrawing substituents on the pK(a) of p-vinyl phenols is due to the delocalized electronic structure of these compounds. Thus, this effect should be additive for multiple substituents attached to the vinylic double bond and quantifiable by LFER-based methods. The aim of this study was to produce an improved equation with a reduced tendency to underestimate the effect of the double bond on the ionisation of the phenolic hydroxyl. To this end a set of 19 para-substituted vinyl phenols was used. The ionisation constants were measured potentiometrically, and a training set of 10 compounds was selected to build a regression model (r2 = 0.987 and S.E. = 0.09). The average error with an external test set of six compounds was 0.19 for our model and 1.27 for the ACD-labs 7.0. Thus, we have been able to significantly improve the existing model for prediction of the ionisation constants of substituted p-vinyl phenols.

Enhancing electron transport in molecular wires by insertion of a ferrocene center.

PubMed

Sun, Yan-Yan; Peng, Zheng-Lian; Hou, Rong; Liang, Jing-Hong; Zheng, Ju-Fang; Zhou, Xiao-Yi; Zhou, Xiao-Shun; Jin, Shan; Niu, Zhen-Jiang; Mao, Bing-Wei

2014-02-14

We have determined the conductance of alkane-linked ferrocene molecules with carboxylic acid anchoring groups using the STM break junction technique, and three sets of conductance values were found, i.e. high conductance (HC), medium conductance (MC) and low conductance (LC) values. The enhancing effect of the incorporated ferrocene on the electron transport in saturated alkane molecular wires is demonstrated by the increased conductance of the ferrocene molecules, attributed to the reduction of the tunneling barrier and the HOMO-LUMO gap induced by the insertion of ferrocene. Furthermore, the electron-withdrawing carbonyl group on the unconjugated backbone has little or no influence on single-molecule conductance. The current work provides a feasible approach for the design of high-performance molecular wires.

Determination of adiabatic ionization potentials and electron affinities of energetic molecules with the Gaussian-4 method

NASA Astrophysics Data System (ADS)

Manaa, M. Riad

2017-06-01

Adiabatic ionization potentials (IPad) and electron affinities (EAad) are determined with the Gaussian-4 (G4) method for the energetic molecules PETN, RDX, β-δ-HMX, CL-17, TNB, TNT, CL-14, DADNE, TNA, and TATB. The IPad and EAad values are in the range of 8.43-11.73 and 0.74-2.86 eV, respectively. Variations are due to substitutional effects of electron withdrawing and donating functional groups. Enthalpies of formation are also determined for several of these molecules to augment the list of recently reported G4 values. The calculated IPad and EAad provide quantitative assessment of such molecular properties as chemical hardness, molecular electronegativity, and "intrinsic" molecular physical hardness.

Estimated use of water in the United States in 2015

USGS Publications Warehouse

Dieter, Cheryl A.; Maupin, Molly A.; Caldwell, Rodney R.; Harris, Melissa A.; Ivahnenko, Tamara I.; Lovelace, John K.; Barber, Nancy L.; Linsey, Kristin S.

2018-06-19

Water use in the United States in 2015 was estimated to be about 322 billion gallons per day (Bgal/d), which was 9 percent less than in 2010. The 2015 estimates put total withdrawals at the lowest level since before 1970, following the same overall trend of decreasing total withdrawals observed from 2005 to 2010. Freshwater withdrawals were 281 Bgal/d, or 87 percent of total withdrawals, and saline-water withdrawals were 41.0 Bgal/d, or 13 percent of total withdrawals. Fresh surface-water withdrawals (198 Bgal/d) were 14 percent less than in 2010, and fresh groundwater withdrawals (82.3 Bgal/day) were about 8 percent greater than in 2010. Saline surface-water withdrawals were 38.6 Bgal/d, or 14 percent less than in 2010. Total saline groundwater withdrawals in 2015 were 2.34 Bgal/d, mostly for mining use.Thermoelectric power and irrigation remained the two largest uses of water in 2015, and total withdrawals decreased for thermoelectric power but increased for irrigation. With­drawals in 2015 for thermoelectric power were 18 percent less and withdrawals for irrigation were 2 percent greater than in 2010. Similarly, other uses showed reductions compared to 2010, specifically public supply (–7 percent), self-supplied domestic (–8 percent), self-supplied industrial (–9 percent), and aquaculture (–16 percent). In addition to irrigation (2 percent), mining (1 percent) reported larger withdrawals in 2015 than in 2010. Livestock withdrawals remained essentially the same in 2015 compared to 2010 (0 percent change). Thermoelectric power, irrigation, and public-supply withdrawals accounted for 90 percent of total withdrawals in 2015.Withdrawals for thermoelectric power were 133 Bgal/d in 2015 and represented the lowest levels since before 1970. Surface-water withdrawals accounted for more than 99 percent of total thermoelectric-power withdrawals, and 72 percent of those surface-water withdrawals were from freshwater sources. Saline surface-water withdrawals for thermoelectric power accounted for 97 percent of total saline surface-water withdrawals for all uses. Thermoelectric-power withdrawals accounted for 41 percent of total withdrawals for all uses, and freshwater withdrawals for thermoelectric power accounted for 34 percent of the total freshwater withdrawals for all uses. Total consumptive use for thermoelectric power was 4.31 Bgal/d in 2015 or 3 percent of the total thermoelectric-power withdrawals.Irrigation withdrawals were 118 Bgal/d in 2015, an increase of 2 percent from 2010 (116 Bgal/d), but were approximately equal to withdrawals estimated in the 1960s. Irrigation withdrawals, all freshwater, accounted for 42 percent of total freshwater withdrawals for all uses and 64 percent of total freshwater withdrawals for all uses excluding thermoelectric power. Surface-water withdrawals (60.9 Bgal/d) accounted for 52 percent of the total irrigation withdrawals, or about 8 percent less than in 2010. Ground­water withdrawals for irrigation were 57.2 Bgal/d in 2015, about 16 percent more than in 2010. About 63,500 thousand acres (or 63.5 million acres) were irrigated in 2015, an increase from 2010 of about 1,130 thousand acres (2 percent). The number of acres irrigated using sprinkler and microirrigation systems accounted for 63 percent of the total irrigated lands in 2015. Total consumptive use for irrigation was 73.2 Bgal/d in 2015 or 62 percent of the total use (withdrawals and reclaimed wastewater).Public-supply withdrawals in 2015 were 39.0 Bgal/d, or 7 percent less than in 2010, continuing the declines observed from 2005 to 2010. Total population in the United States increased from 312.6 million people in 2010 to 325.0 million people in 2015, an increase of 4 percent. Public-supply withdrawals accounted for 14 percent of the total freshwater withdrawals for all uses and 21 percent of freshwater with­drawals for all uses, excluding thermoelectric power. The number of people that received potable water from public-supply facilities in 2015 was 283 million, or about 87 percent of the total United States population. This percentage is 1 percent greater than in 2010. Self-supplied domestic withdrawals were 3.26 Bgal/d, or 8 percent less than in 2010. More than 98 percent of the self-supplied domestic withdrawals were from groundwater sources.Self-supplied industrial withdrawals were 14.8 Bgal/d in 2015, a 9 percent decline from 2010, continuing the downward trend since the peak of 47 Bgal/d in 1970. Total self-supplied industrial withdrawals were 5 percent of total withdrawals for all uses and 8 percent of total withdrawals for all uses, excluding thermoelectric power. Most of the total self-supplied industrial withdrawals were from surface-water sources (82 percent), and nearly all (94 percent) of those surface-water withdrawals were from freshwater sources. Nearly all of the groundwater withdrawals for self-supplied industrial use (98 percent) were from freshwater sources.Total aquaculture withdrawals were 7.55 Bgal/d in 2015, or 16 percent less than in 2010, and surface water was the primary source (79 percent). Most of the surface-water withdrawals occurred at facilities that operated flow-through raceways, which returned the water to the source directly after use. Aquaculture withdrawals accounted for 2 percent of the total withdrawals for all uses and 4 percent of the total withdrawals for all uses, excluding thermoelectric.Total mining withdrawals in 2015 were 4.00 Bgal/d, or about 1 percent of total withdrawals from all uses and 2 percent of total withdrawals from all uses, excluding thermoelectric. Mining withdrawals increased 1 percent from 2010 to 2015. Groundwater withdrawals accounted for 72 percent of the total mining withdrawals, and most of the groundwater was saline (65 percent). Most (77 percent) of the surface-water withdrawals for mining was freshwater.Livestock withdrawals in 2015 were 2.00 Bgal/d, the same as in 2010. All livestock withdrawals were from freshwater sources, mostly from groundwater (62 percent). Livestock withdrawals accounted for about 1 percent of total freshwater withdrawals for all uses, excluding thermoelectric power.In 2015, more than 50 percent of the total withdrawals in the United States were accounted for by 12 States (California, Texas, Idaho, Florida, Arkansas, New York, Illinois, Colorado, North Carolina, Michigan, Montana, and Nebraska). California accounted for almost 9 percent of the total withdrawals and 9 percent of freshwater withdrawals in the United States, predominantly for irrigation. Texas accounted for almost 7 percent of total withdrawals, predominantly for thermoelectric power, irrigation, and public supply. Florida accounted for 23 percent of the total saline-water withdrawals in the United States, mostly from surface-water sources for thermoelectric power. Texas and California accounted for 59 percent of the total saline groundwater withdrawals in the United States, mostly for mining.

Effect of chronic usage of tramadol on motor cerebral cortex and testicular tissues of adult male albino rats and the effect of its withdrawal: histological, immunohistochemical and biochemical study.

PubMed

Ghoneim, Fatma M; Khalaf, Hanaa A; Elsamanoudy, Ayman Z; Helaly, Ahmed N

2014-01-01

This study was designed to demonstrate the histopathological and biochemical changes in rat cerebral cortex and testicles due to chronic usage of tramadol and the effect of withdrawal. Thirty adult male rats weighing 180-200 gm were classified into three groups; group I (control group) group II (10 rats received 50 mg/kg/day of tramadol intraperitoneally for 4 weeks) and group III (10 rats received the same dose as group II then kept 4 weeks later to study the effect of withdrawal). Histological and immunohistochemical examination of cerebral cortex and testicular specimens for Bax (apoptotic marker) were carried out. Testicular specimens were examined by electron microscopy. RT-PCR after RNA extraction from both specimens was done for the genes of some antioxidant enzymes .Also, malondialdehyde (MDA) was measured colourimetrically in tissues homogenizate. The results of this study demonstrated histological changes in testicular and brain tissues in group II compared to group I with increased apoptotic index proved by increased Bax expression. Moreover in this group increased MDA level with decreased gene expression of the antioxidant enzymes revealed oxidative stress. Group III showed signs of improvement but not returned completely normal. It could be concluded that administration of tramadol have histological abnormalities on both cerebral cortex and testicular tissues associated with oxidative stress in these organs. Also, there is increased apoptosis in both organs which regresses with withdrawal. These findings may provide a possible explanation for delayed fertility and psychological changes associated with tramadol abuse.

Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna–C60 contact and effective photodynamic potential†

PubMed Central

Padmawar, Prashant A.; Rogers-Haley, Joy E.; So, Grace; Canteenwala, Taizoon; Thota, Sammaiah; Tan, Loon-Seng; Pritzker, Kenneth; Huang, Ying-Ying; Sharma, Sulbha K.; Kurup, Divya Balachandran; Hamblin, Michael R.; Wilson, Brian; Urbas, Augustine

2010-01-01

We report the synthesis of a new class of photoresponsive C60–DCE–diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C60(>DPAF-Cn) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C60(>CPAF-Cn) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C60–DCE–DPAF nanostructures to longer red wavelengths than C60(>DPAF-Cn). Accordingly, C60(>CPAF-Cn) may allow 2γ-PDT using a light wavelength of 1000–1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C60(>DPAF-C2M) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the 1O2 quantum yield of C60(>CPAF-C2M) was found to be nearly 6-fold higher than that of C60(>DPAF-C2M), demonstrating the large light-harvesting enhancement of the CPAF-C2M moiety and leading to more efficient triplet state generation of the C60> cage moiety. This led to highly effective killing of HeLa cells by C60(>CPAF-C2M) via photodynamic therapy (200 J cm−2 white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group. PMID:20890406

Dendritic azo compounds as a new type amorphous molecular material with quick photoinduced surface-relief-grating formation ability

NASA Astrophysics Data System (ADS)

He, Yaning; Gu, Xinyu; Guo, Miaocai; Wang, Xiaogong

2008-09-01

A series of dendritic azobenzene-containing compounds have been synthesized as a new type amorphous molecular material, which can show quick surface-relief-grating (SRG) formation ability upon light irradiation. For the synthesis, the dendritic precursor tris(2-(ethyl(phenyl)amino)ethyl)benzene-1,3,5-tricarboxylate and tris(3,5-bis(2-(ethyl(phenyl)amino)ethoxy)benzyl)benzene-1,3,5-tricarboxylate were prepared by esterification reactions between 1,3,5-benzenetricarbonyl chloride and N-ethyl- N-hydroxyethyl-aniline and 3,5-bis[2-( N-ethylanilino)ethoxy] benzylalcohol. The precursors were, respectively reacted with the diazonium salts of 4-nitroaniline, 4-aminobenzoic acid, and 4-aminobenzonitrile to introduce different types of donor-acceptor azo chromophores at the peripheral positions. The structure and properties of the dendritic azo compounds were characterized by the spectroscopic methods and thermal analysis. The surface-relief-grating (SRG) formation behavior of the dendritic azo compounds was studied by exposing the spin-coated thin films to an interference pattern of laser beams (532 nm) at modest intensity (100 mW/cm 2). The results show that the azo compounds can form stable amorphous glasses in a broad temperature range. The glass transition temperatures ( Tgs) depend on the backbone structures and the type of the peripheral azo chromophors. The type of the electron withdrawing groups in the p-positions of the terminal azobenzene units shows a significant influence on the SRG inscription rate. For the compounds containing the same type azo chromophores, the SRG inscription rate is also affected by the backbone structure.

Spontaneous Formation of Nanopatterns in Velocity-Dependent Dip-Coated Organic Films: From Dragonflies to Stripes

NASA Astrophysics Data System (ADS)

Huber, P.; Bai, M.; Del Campo, V.; Homm, P.; Ferrari, P.; Diama, A.; Wagner, C.; Taub, H.; Knorr, K.; Deutsch, M.; Retamal, M.; Volkmann, U.; Corrales, T.

2015-11-01

We present the structure of thin, n-alkane films on the oxide layer of a silicon surface, prepared by dip-coating in a n-C32H66/n-heptane solution. Electron micrographs reveal two adsorption morphologies depending on the substrate withdrawal speed v. For small v, dragonfly-shaped molecular islands are observed. For a large v, stripes parallel to the withdrawal direction are observed. These have a few hundred micrometer lengths and a few-micrometer lateral separation. With increasing v, the surface coverage first decreases, then increases for v >vcr ~ 0 . 15 mm/s. The critical vcr marks a transition between the evaporation regime and the entrainment regime. The stripes' strong crystalline texture and the well defined separation are due to an anisotropic 2D crystallization in narrow liquid fingers, which presumably results from a Marangoni-flow-driven hydrodynamic instability in the evaporating dip-coated films.

Electron attachment to trinitrotoluene (TNT) embedded in He droplets: complete freezing of dissociation intermediates in an extended range of electron energies.

PubMed

Mauracher, Andreas; Schöbel, Harald; Ferreira da Silva, Filipe; Edtbauer, Achim; Mitterdorfer, Christian; Denifl, Stephan; Märk, Tilmann D; Illenberger, Eugen; Scheier, Paul

2009-10-01

Electron attachment to the explosive trinitrotoluene (TNT) embedded in Helium droplets (TNT@He) generates the non-decomposed complexes (TNT)(n)(-), but no fragment ions in the entire energy range 0-12 eV. This strongly contrasts the behavior of single TNT molecules in the gas phase at ambient temperatures, where electron capture leads to a variety of different fragmentation products via different dissociative electron attachment (DEA) reactions. Single TNT molecules decompose by attachment of an electron at virtually no extra energy reflecting the explosive nature of the compound. The complete freezing of dissociation intermediates in TNT embedded in the droplet is explained by the particular mechanisms of DEA in nitrobenzenes, which is characterized by complex rearrangement processes in the transient negative ion (TNI) prior to decomposition. These mechanisms provide the condition for effective energy withdrawal from the TNI into the dissipative environment thereby completely suppressing its decomposition.

Posttranscriptional Upregulation of IDH1 by HuR Establishes a Powerful Survival Phenotype in Pancreatic Cancer Cells

PubMed Central

Zarei, Mahsa; Lal, Shruti; Parker, Seth J.; Nevler, Avinoam; Vaziri-Gohar, Ali; Dukleska, Katerina; Mambelli-Lisboa, Nicole C.; Moffat, Cynthia; Blanco, Fernando F.; Chand, Saswati N.; Jimbo, Masaya; Cozzitorto, Joseph A.; Jiang, Wei; Yeo, Charles J.; Londin, Eric R.; Seifert, Erin L.; Metallo, Christian M.; Brody, Jonathan R.; Winter, Jordan M.

2018-01-01

Cancer aggressiveness may result from the selective pressure of a harsh nutrient-deprived microenvironment. Here we illustrate how such conditions promote chemotherapy resistance in pancreatic ductal adenocarcinoma (PDAC). Glucose or glutamine withdrawal resulted in a 5- to 10-fold protective effect with chemotherapy treatment. PDAC xenografts were less sensitive to gemcitabine in hypoglycemic mice compared with hyperglycemic mice. Consistent with this observation, patients receiving adjuvant gemcitabine (n = 107) with elevated serum glucose levels (HgbA1C > 6.5%) exhibited improved survival. We identified enhanced antioxidant defense as a driver of chemoresistance in this setting. ROS levels were doubled in vitro by either nutrient withdrawal or gemcitabine treatment, but depriving PDAC cells of nutrients before gemcitabine treatment attenuated this effect. Mechanistic investigations based on RNAi or CRISPR approaches implicated the RNA binding protein HuR in preserving survival under nutrient withdrawal, with or without gemcitabine. Notably, RNA deep sequencing and functional analyses in HuR-deficient PDAC cell lines identified isocitrate dehydrogenase 1 (IDH1) as the sole antioxidant enzyme under HuR regulation. HuR-deficient PDAC cells lacked the ability to engraft successfully in immunocompromised mice, but IDH1 overexpression in these cells was sufficient to fully restore chemoresistance under low nutrient conditions. Overall, our findings highlight the HuR–IDH1 regulatory axis as a critical, actionable therapeutic target in pancreatic cancer. PMID:28652247

[Perception by teenagers and adults of the changed by amplitude sound sequences used in models of movement of the sound source].

PubMed

Andreeva, I G; Vartanian, I A

2012-01-01

The ability to evaluate direction of amplitude changes of sound stimuli was studied in adults and in the 11-12- and 15-16-year old teenagers. The stimuli representing sequences of fragments of the tone of 1 kHz, whose amplitude is changing with time, are used as model of approach and withdrawal of the sound sources. The 11-12-year old teenagers at estimation of direction of amplitude changes were shown to make the significantly higher number of errors as compared with two other examined groups, including those in repeated experiments. The structure of errors - the ratio of the portion of errors at estimation of increasing and decreasing by amplitude stimulus - turned out to be different in teenagers and in adults. The question is discussed about the effect of unspecific activation of the large hemisphere cortex in teenagers on processes if taking solution about the complex sound stimulus, including a possibility estimation of approach and withdrawal of the sound source.

2,3-Dihydroxybenzoic acid amides of tetraazaalkanes and tetaaza cycloalkanes

DOEpatents

Weitl, Frederick L. [Martinez, CA; Raymond, Kenneth N. [Berkeley, CA

1980-01-01

A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

Solar photochemical oxidations of benzylic and allylic alcohols using catalytic organo-oxidation with DDQ: application to lignin models.

PubMed

Walsh, Katie; Sneddon, Helen F; Moody, Christopher J

2014-10-03

Visible light has a dramatic effect on the oxidation of benzylic and allylic alcohols, including those deactivated by electron-withdrawing groups, and β-O-4 lignin models, using catalytic amounts of the organo-oxidant 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Sodium nitrite or tert-butyl nitrite is used as cocatalyst, and oxygen is employed as the terminal oxidant.

A novel base-induced isomerization gives access to unprecedented (E)-exo-glycals.

PubMed

Eppe, Guillaume; Dumitrescu, Lidia; Pierrot, Olivier; Li, Tianlei; Pan, Weidong; Vincent, Stéphane P

2013-08-26

Bump the base: This study reports the discovery of the base-induced Z-to-E isomerization of exo-glycals bearing an electron-withdrawing group (EWG). The scope of this novel transformation regarding the carbohydrate unit is also discussed. After elucidating the mechanism, preparation of novel (E)-exo- glycals was performed (TBS = tert-butyldimethylsilyl). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Halogenated Pyrazine-Based Chalcones as Potential Antimicrobial Drugs.

PubMed

Kucerova-Chlupacova, Marta; Vyskovska-Tyllova, Veronika; Richterova-Finkova, Lenka; Kunes, Jiri; Buchta, Vladimir; Vejsova, Marcela; Paterova, Pavla; Semelkova, Lucia; Jandourek, Ondrej; Opletalova, Veronika

2016-10-27

Chalcones, i.e., compounds with the chemical pattern of 1,3-diphenylprop-2-en-1-ones, exert a wide range of bio-activities, e.g., antioxidant, anti-inflammatory, anticancer, anti-infective etc. Our research group has been focused on pyrazine analogues of chalcones; several series have been synthesized and tested in vitro on antifungal and antimycobacterial activity. The highest potency was exhibited by derivatives with electron withdrawing groups (EWG) in positions 2 and 4 of the ring B. As halogens also have electron withdrawing properties, novel halogenated derivatives were prepared by Claisen-Schmidt condensation. All compounds were submitted for evaluation of their antifungal and antibacterial activity, including their antimycobacterial effect. In the antifungal assay against eight strains of selected fungi, growth inhibition of Candida glabrata and Trichophyton interdigitale (formerly T. mentagrophytes ) was shown by non-alkylated derivatives with 2-bromo or 2-chloro substitution. In the panel of selected bacteria, 2-chloro derivatives showed the highest inhibitory effect on Staphylococcus sp. In addition, all products were also screened for their antimycobacterial activity against Mycobacterium tuberculosis H37RV My 331/88, M. kansasii My 235/80, M. avium 152/80 and M. smegmatis CCM 4622. Some of the examined compounds, inhibited growth of M. kansasii and M. smegmatis with minimum inhibitory concentrations (MICs) comparable with those of isoniazid.

Non-Fullerene Electron Acceptors for Use in Organic Solar Cells

PubMed Central

2015-01-01

Conspectus The active layer in a solution processed organic photovoltaic device comprises a light absorbing electron donor semiconductor, typically a polymer, and an electron accepting fullerene acceptor. Although there has been huge effort targeted to optimize the absorbing, energetic, and transport properties of the donor material, fullerenes remain as the exclusive electron acceptor in all high performance devices. Very recently, some new non-fullerene acceptors have been demonstrated to outperform fullerenes in comparative devices. This Account describes this progress, discussing molecular design considerations and the structure–property relationships that are emerging. The motivation to replace fullerene acceptors stems from their synthetic inflexibility, leading to constraints in manipulating frontier energy levels, as well as poor absorption in the solar spectrum range, and an inherent tendency to undergo postfabrication crystallization, resulting in device instability. New acceptors have to address these limitations, providing tunable absorption with high extinction coefficients, thus contributing to device photocurrent. The ability to vary and optimize the lowest unoccupied molecular orbital (LUMO) energy level for a specific donor polymer is also an important requirement, ensuring minimal energy loss on electron transfer and as high an internal voltage as possible. Initially perylene diimide acceptors were evaluated as promising acceptor materials. These electron deficient aromatic molecules can exhibit good electron transport, facilitated by close packed herringbone crystal motifs, and their energy levels can be synthetically tuned. The principal drawback of this class of materials, their tendency to crystallize on too large a length scale for an optimal heterojunction nanostructure, has been shown to be overcome through introduction of conformation twisting through steric effects. This has been primarily achieved by coupling two units together, forming dimers with a large intramolecular twist, which suppresses both nucleation and crystal growth. The generic design concept of rotationally symmetrical aromatic small molecules with extended π orbital delocalization, including polyaromatic hydrocarbons, phthalocyanines, etc., has also provided some excellent small molecule acceptors. In most cases, additional electron withdrawing functionality, such as imide or ester groups, can be incorporated to stabilize the LUMO and improve properties. New calamitic acceptors have been developed, where molecular orbital hybridization of electron rich and poor segments can be judiciously employed to precisely control energy levels. Conformation and intermolecular associations can be controlled by peripheral functionalization leading to optimization of crystallization length scales. In particular, the use of rhodanine end groups, coupled electronically through short bridged aromatic chains, has been a successful strategy, with promising device efficiencies attributed to high lying LUMO energy levels and subsequently large open circuit voltages. PMID:26505279

Application of two-dimensional binary fingerprinting methods for the design of selective Tankyrase I inhibitors.

PubMed

Muddukrishna, B S; Pai, Vasudev; Lobo, Richard; Pai, Aravinda

2017-11-22

In the present study, five important binary fingerprinting techniques were used to model novel flavones for the selective inhibition of Tankyrase I. From the fingerprints used: the fingerprint atom pairs resulted in a statistically significant 2D QSAR model using a kernel-based partial least square regression method. This model indicates that the presence of electron-donating groups positively contributes to activity, whereas the presence of electron withdrawing groups negatively contributes to activity. This model could be used to develop more potent as well as selective analogues for the inhibition of Tankyrase I. Schematic representation of 2D QSAR work flow.

Implications of vegetation hydraulic capacitance as an indicator of water stress and drought recovery

NASA Astrophysics Data System (ADS)

Matheny, A. M.; Bohrer, G.

2017-12-01

Above-ground water storage in vegetation plays an integral role in the avoidance of hydraulic impairment to transpiration. New high temporal resolution measurements of dynamic changes in tree hydraulic capacitance are facilitating insights into vegetation water use strategies. Diurnal withdrawal from water storage in leaves, branches, stems, and roots significantly impacts sap flow, stomatal conductance, and transpiration. The ability to store and use water varies based on soil- and root-water availability, tree size, wood vessel anatomy and density, and stomatal response strategy (i.e. isohydricity). We present results from a three-year long study of stem capacitance dynamics in five species in a mixed deciduous forest in Michigan. The site receives 800mm of rainfall annually, but water potential in the well-drained sandy soil nears the permanent wilting point several times annually. We demonstrate radical differences in stored water use between drought tolerant and intolerant species. Red maple, a drought intolerant, isohydric species, showed a strong dependence on stem capacitance for transpiration during both wet and dry periods. Red oak, a more drought hearty, deep rooted, anisohydric species, was much less reliant on withdrawal from water storage during all conditions. During well-watered conditions, withdrawal from storage by red maple was 10 kg day-1, yet storage withdrawal from similarly sized red oaks was 1 kg day-1. Red oaks only drew strongly upon stored water during the driest extremes. Metrics of hydration status derived from capacitance provide a means to explore drought response and recovery. Declines in consecutive days' maximum capacitance indicate an inability to restore lost water and can be used to mark the onset of water stress. Drought recovery can be quantified as the time required for stem water content to return to pre-drought volumes. Capacitance withdrawal and depletion exhibit a clear threshold response to declining soil water availability. These new measurement technologies will also improve our understanding of trees' water status regulation in response to drying soil and drought, and could improve plant hydrodynamic modeling.

Motor impairment: a new ethanol withdrawal phenotype in mice

PubMed Central

Philibin, Scott D.; Cameron, Andy J.; Metten, Pamela; Crabbe, John C.

2015-01-01

Alcoholism is a complex disorder with genetic and environmental risk factors. The presence of withdrawal symptoms is one criterion for alcohol dependence. Genetic animal models have followed a reductionist approach by quantifying various effects of ethanol withdrawal separately. Different ethanol withdrawal symptoms may have distinct genetic etiologies, and therefore differentiating distinct neurobiological mechanisms related to separate signs of withdrawal would increase our understanding of various aspects of the complex phenotype. This study establishes motor incoordination as a new phenotype of alcohol withdrawal in mice. Mice were made physically dependent on ethanol by exposure to ethanol vapor for 72 h. The effects of ethanol withdrawal in mice from different genetic backgrounds were measured on the accelerating rotarod, a simple motor task. Ethanol withdrawal disrupted accelerating rotarod behavior in mice. The disruptive effects of withdrawal suggest a performance rather than a learning deficit. Inbred strain comparisons suggest genetic differences in magnitude of this withdrawal phenotype. The withdrawal-induced deficits were not correlated with the selection response difference in handling convulsion severity in selectively bred Withdrawal Seizure-Prone and Withdrawal Seizure-Resistant lines. The accelerating rotarod seems to be a simple behavioral measure of ethanol withdrawal that is suitable for comparing genotypes. PMID:18690115

Simulation of groundwater flow to assess future withdrawals associated with Base Realignment and Closure (BRAC) at Fort George G. Meade, Maryland

USGS Publications Warehouse

Raffensperger, Jeff P.; Fleming, Brandon J.; Banks, William S.L.; Horn, Marilee A.; Nardi, Mark R.; Andreasen, David C.

2010-01-01

Increased groundwater withdrawals from confined aquifers in the Maryland Coastal Plain to supply anticipated growth at Fort George G. Meade (Fort Meade) and surrounding areas resulting from the Department of Defense Base Realignment and Closure Program may have adverse effects in the outcrop or near-outcrop areas. Specifically, increased pumping from the Potomac Group aquifers (principally the Patuxent aquifer) could potentially reduce base flow in small streams below rates necessary for healthy biological functioning. Additionally, water levels may be lowered near, or possibly below, the top of the aquifer within the confined-unconfined transition zone near the outcrop area. A three-dimensional groundwater flow model was created to incorporate and analyze data on water withdrawals, streamflow, and hydraulic head in the region. The model is based on an earlier model developed to assess the effects of future withdrawals from well fields in Anne Arundel County, Maryland and surrounding areas, and includes some of the same features, including model extent, boundary conditions, and vertical discretization (layering). The resolution (horizontal grid discretization) of the earlier model limited its ability to simulate the effects of withdrawals on the outcrop and near-outcrop areas. The model developed for this study included a block-shaped higher-resolution local grid, referred to as the child model, centered on Fort Meade, which was coupled to the coarser-grid parent model using the shared node Local Grid Refinement capability of MODFLOW-LGR. A more detailed stream network was incorporated into the child model. In addition, for part of the transient simulation period, stress periods were reduced in length from 1 year to 3 months, to allow for simulation of the effects of seasonally varying withdrawals and recharge on the groundwater-flow system and simulated streamflow. This required revision of the database on withdrawals and estimation of seasonal variations in recharge represented in the earlier model. The calibrated model provides a tool for future forecasts of changes in the system under different management scenarios, and for simulating potential effects of withdrawals at Fort Meade and the surrounding area on water levels in the near-outcrop area and base flow in the outcrop area. Model error was assessed by comparing observed and simulated water levels from 62 wells (55 in the parent model and 7 in the child model). The root-mean-square error values for the parent and child model were 8.72 and 11.91 feet, respectively. Root-mean-square error values for the 55 parent model observation wells range from 0.95 to 30.31 feet; the range for the 7 child model observation wells is 5.00 to 24.17 feet. Many of the wells with higher root-mean-square error values occur at the perimeter of the child model and near large pumping centers, as well as updip in the confined aquifers. Root-mean-square error values decrease downdip and away from the large pumping centers. Both the parent and child models are sensitive to increasing withdrawal rates. The parent model is more sensitive than the child model to decreasing transmissivity of layers 3, 4, 5, and 6. The parent model is relatively insensitive to riverbed vertical conductance, however, the child model does exhibit some sensitivity to decreasing riverbed conductance. The overall water budget for the model included sources and sinks of water including recharge, surface-water bodies and rivers and streams, general-head boundaries, and withdrawals from permitted wells. Withdrawal from wells in 2005 was estimated to be equivalent to 8.5 percent of the total recharge rate.

Withdrawal: Expanding a Key Addiction Construct

PubMed Central

2015-01-01

Withdrawal is an essential component of classical addiction theory; it is a vital manifestation of dependence and motivates relapse. However, the traditional conceptualization of withdrawal as a cohesive collection of symptoms that emerge during drug deprivation and decline with either the passage of time or reinstatement of drug use, may be inadequate to explain scientific findings or fit with modern theories of addiction. This article expands the current understanding of tobacco withdrawal by examining: (1) withdrawal variability; (2) underlying causes of withdrawal variability, including biological and person factors, environmental influences, and the influence of highly routinized behavioral patterns; (3) new withdrawal symptoms that allow for enhanced characterization of the withdrawal experience; and (4) withdrawal-related cognitive processes. These topics provide guidance regarding the optimal assessment of withdrawal and illustrate the potential impact modern withdrawal conceptualization and assessment could have on identifying treatment targets. PMID:25744958

Free radical generation from an aniline derivative in HepG2 cells: a possible captodative effect.

PubMed

Horinouchi, Yuya; Summers, Fiona A; Ehrenshaft, Marilyn; Mason, Ronald P

2015-01-01

Xenobiotic metabolism can induce the generation of protein radicals, which are believed to play an important role in the toxicity of chemicals and drugs. It is therefore important to identify chemical structures capable of inducing macromolecular free radical formation in living cells. In this study, we evaluated the ability of four structurally related environmental chemicals, aniline, nitrosobenzene, N,N-dimethylaniline, and N,N-dimethyl-4-nitrosoaniline (DMNA), to induce free radicals and cellular damage in the hepatoma cell line HepG2. Cytotoxicity was assessed using lactate dehydrogenase assays, and morphological changes were observed using phase contrast microscopy. Protein free radicals were detected by immuno-spin trapping using in-cell western experiments and confocal microscopy to determine the subcellular locale of free radical generation. DMNA induced free radical generation, lactate dehydrogenase release, and morphological changes in HepG2 cells, whereas aniline, nitrosobenzene, N,N-dimethylaniline did not. Confocal microscopy showed that DMNA induced free radical generation mainly in the cytosol. Preincubation of HepG2 cells with N-acetylcysteine and 2,2'-dipyridyl significantly prevented free radical generation on subsequent incubation with DMNA, whereas preincubation with apocynin and dimethyl sulfoxide had no effect. These results suggest that DMNA is metabolized to reactive free radicals capable of generating protein radicals which may play a critical role in DMNA toxicity. We propose that the captodative effect, the combined action of the electron-releasing dimethylamine substituent, and the electron-withdrawing nitroso substituent, leads to a thermodynamically stabilized radical, facilitating enhanced protein radical formation by DMNA. Copyright © 2014 Elsevier Inc. All rights reserved.

MULTIPLE ELECTRON BEAM ION PUMP AND SOURCE

DOEpatents

Ellis, R.E.

1962-02-27

A vacuum pump is designed which operates by ionizing incoming air and by withdrawing the ions from the system by means of electrical fields. The apparatus comprises a cylindrical housing communicable with the vessel to be evacuated and having a thin wall section in one end. Suitable coils provide a longitudinal magnetic field within the cylinder. A broad cathode and an anode structure is provided to establish a plurality of adjacent electron beams which are parallel to the cylinder axis. Electron reflector means are provided so that each of the beams constitutes a PIG or reflex discharge. Such structure provides a large region in which incoming gas molecules may be ionized by electron bombardment. A charged electrode assembly accelerates the ions through the thin window, thereby removing the gas from the system. The invention may also be utilized as a highly efficient ion source. (AEC)

Electronic structure of some adenosine receptor antagonists. III. Quantitative investigation of the electronic absorption spectra of alkyl xanthines

NASA Astrophysics Data System (ADS)

Moustafa, H.; Shalaby, Samia H.; El-sawy, K. M.; Hilal, Rifaat

2002-07-01

Quantitative and comparative investigation of the electronic absorption spectra of theophylline, caffeine and their derivatives is reported. The spectra of theophylline, caffeine and theobromine were compared to establish the predominant tautomeric species in solution. This comparison, analysis of solvent effects and assignments of the observed transitions via MO computations indicate the exits of only one tautomeric species in solution that is the N7 form. A low-lying triplet state was identified which corresponds to a HOMO-LUMO transition. This relatively long-lived T 1 state is always less polar than the ground state and may very well underlie the photochemical reactivity of alkyl xanthines. Substituents of different electron donating or withdrawing strengths and solvent effects are investigated and analyzed. The present analysis is facilitated via computer deconvolution of the observed spectra and MO computation.

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

Modulation of ethanol withdrawal-induced anxiety-like behavior during later withdrawals by treatment of early withdrawals with benzodiazepine/gamma-aminobutyric acid ligands.

PubMed

Knapp, Darin J; Overstreet, David H; Breese, George R

2005-04-01

Anxiety states, including those arising during acute or protracted withdrawal periods, may be precipitating factors in alcoholic relapse. Given the cyclical nature of ethanol withdrawal associated with repeated cycles of ethanol intake and abstinence in a pattern that often spans years, meaningful attempts to model ethanol withdrawal-associated anxiety should incorporate cycled ethanol treatments. The studies reported herein examined the effects of gamma-aminobutyric acid-modulating drugs on social interaction behavior-an established model of anxiety-in rats exposed to repeated cycles of ethanol treatment and withdrawal. Rats were exposed to 8 to 12 g/kg/day ethanol during three 7-day dietary cycles (5 days on ethanol diet followed by 2 days on control diet). Ethanol was administered either at hour 4 of withdrawal after cessation of each of the first 2 ethanol cycles or during the final withdrawal only. In other groups, the early withdrawals were treated with alphaxalone, diazepam, PK11159, or flumazenil to block anxiety-like behavior during an untreated later (third) withdrawal. The benzodiazepine inverse agonist DMCM (methyl-6, 7-dymerhoxy-4-ethyl-beta-carboline-3-carboxylate) was also given repeatedly to determine whether it would sensitize anxiety-like behavior during a future withdrawal. Finally, the effects of all drugs on deficits in locomotor behavior were assessed. Pretreatment of earlier withdrawals with alphaxalone, diazepam, ethanol, or flumazenil reduced social interaction deficits during a later withdrawal, but pretreatment with PK11195 did not. In contrast, DMCM administered in lieu of early withdrawals increased social interaction deficits during an untreated later withdrawal. Locomotor deficits were significantly reversed only by the acute ethanol and diazepam treatment during the final withdrawal. Single-dose administration of drugs that enhance or diminish activity at benzodiazepine-gamma-aminobutyric acid- receptors during earlier withdrawals reduced or potentiated, respectively, anxiety-like behavior during later, drug-free withdrawals. These results support the potential of the novel strategy of using prophylactic therapy administered during early withdrawals to ameliorate symptoms of later withdrawals.

Development and calibration of a ground-water flow model for the Sparta Aquifer of southeastern Arkansas and north-central Louisiana and simulated response to withdrawals, 1998-2027

USGS Publications Warehouse

McKee, Paul W.; Clark, Brian R.

2003-01-01

The Sparta aquifer, which consists of the Sparta Sand, in southeastern Arkansas and north-central Louisiana is a major water resource and provides water for municipal, industrial, and agricultural uses. In recent years, the demand in some areas has resulted in withdrawals from the Sparta aquifer that substantially exceed replenishment of the aquifer. Considerable drawdown has occurred in the potentiometric surface forming regional cones of depression as water is removed from storage by withdrawals. These cones of depression are centered beneath the Grand Prairie area and the cities of Pine Bluff and El Dorado in Arkansas, and Monroe in Louisiana. The rate of decline for hydraulic heads in the aquifer has been greater than 1 foot per year for more than a decade in much of southern Arkansas and northern Louisiana where hydraulic heads are now below the top of the Sparta Sand. Continued hydraulic-head declines have caused water users and managers alike to question the ability of the aquifer to supply water for the long term. Concern over protecting the Sparta aquifer as a sustainable resource has resulted in a continued, cooperative effort by the Arkansas Soil and Water Conservation Commission, U.S. Army Corps of Engineers, and the U.S. Geological Survey to develop, maintain, and utilize numerical ground-water flow models to manage and further analyze the ground-water system. The work presented in this report describes the development and calibration of a ground-water flow model representing the Sparta aquifer to simulate observed hydraulic heads, documents major differences in the current Sparta model compared to the previous Sparta model calibrated in the mid-1980's, and presents the results of three hypothetical future withdrawal scenarios. The current Sparta model-a regional scale, three-dimensional numerical ground-water flow model-was constructed and calibrated using available hydrogeologic, hydraulic, and water-use data from 1898 to 1997. Significant changes from the previous model include grid rediscretization of the aquifer, extension of the active model area northward beyond the Cane River Formation facies change, and representation of model boundaries. The current model was calibrated with the aid of parameter estimation, a nonlinear regression technique, combined with trial and error parameter adjustment using a total of 795 observations from 316 wells over 4 different years-1970, 1985, 1990, and 1997. The calibration data set provides broad spatial and temporal coverage of aquifer conditions. Analysis of the residual statistics, spatial distribution of residuals, simulated compared to observed hydrographs, and simulated compared to observed potentiometric surfaces were used to analyze the ability of the calibrated model to simulate aquifer conditions within acceptable error. The calibrated model has a root mean square error of 18 feet for all observations, an improvement of more than 12 feet from the previous model. The current Sparta model was used to predict the effects of three hypothetical withdrawal scenarios on hydraulic heads over the period 1998-2027 with one of those extended indefinitely until equilibrium conditions were attained, or steady state. In scenario 1a, withdrawals representing the time period from 1990 to 1997 was held constant for 30 years from 1998 to 2027. Hydraulic heads in the middle of the cone of depression centered on El Dorado decreased by 10 feet from the 1997 simulation to 222 feet below NGVD of 1929 in 2027. Hydraulic heads in the Pine Bluff cone of depression showed a greater decline from 61 feet below NGVD of 1929 to 78 feet below NGVD of 1929 in the center of the cone. With these same withdrawals extended to steady state (scenario 1b), hydraulic heads in the Pine Bluff cone of depression center declined an 2 Development and Calibration of a Ground-Water Flow Model for the Sparta Aquifer of Southeastern Arkansas and North-Central Louisiana and Simulated Response to Withdrawa

19 CFR 144.27 - Withdrawal from warehouse by transferee.

Code of Federal Regulations, 2012 CFR

2012-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) WAREHOUSE AND REWAREHOUSE ENTRIES AND WITHDRAWALS Transfer of Right To Withdraw Merchandise from Warehouse § 144.27 Withdrawal from warehouse by transferee. At any time within... withdraw all or part of the merchandise covered by the transfer by filing any authorized kind of withdrawal...

19 CFR 144.27 - Withdrawal from warehouse by transferee.

Code of Federal Regulations, 2010 CFR

2010-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) WAREHOUSE AND REWAREHOUSE ENTRIES AND WITHDRAWALS Transfer of Right To Withdraw Merchandise from Warehouse § 144.27 Withdrawal from warehouse by transferee. At any time within... withdraw all or part of the merchandise covered by the transfer by filing any authorized kind of withdrawal...

Different Effect of the Additional Electron-Withdrawing Cyano Group in Different Conjugation Bridge: The Adjusted Molecular Energy Levels and Largely Improved Photovoltaic Performance.

PubMed

Li, Huiyang; Fang, Manman; Hou, Yingqin; Tang, Runli; Yang, Yizhou; Zhong, Cheng; Li, Qianqian; Li, Zhen

2016-05-18

Four organic sensitizers (LI-68-LI-71) bearing various conjugated bridges were designed and synthesized, in which the only difference between LI-68 and LI-69 (or LI-70 and LI-71) was the absence/presence of the CN group as the auxiliary electron acceptor. Interestingly, compared to the reference dye of LI-68, LI-69 bearing the additional CN group exhibited the bad performance with the decreased Jsc and Voc values. However, once one thiophene moiety near the anchor group was replaced by pyrrole with the electron-rich property, the resultant LI-71 exhibited a photoelectric conversion efficiency increase by about 3 folds from 2.75% (LI-69) to 7.95% (LI-71), displaying the synergistic effect of the two moieties (CN and pyrrole). Computational analysis disclosed that pyrrole as the auxiliary electron donor (D') in the conjugated bridge can compensate for the lower negative charge in the electron acceptor, which was caused by the CN group as the electron trap, leading to the more efficient electron injection and better photovoltaic performance.

Gender differences in self-reported withdrawal symptoms and reducing or quitting smoking three years later: A prospective, longitudinal examination of U.S. adults

PubMed Central

Weinberger, Andrea H.; Platt, Jonathan; Shuter, Jonathan; Goodwin, Renee D.

2016-01-01

Background Little is known about gender differences in withdrawal symptoms among smokers in the community. This study used longitudinal epidemiologic data to examine gender differences in current smokers’ report of withdrawal symptoms during past quit attempts and the relationship between withdrawal symptoms and the odds of reducing or quitting smoking three years later. Methods Data were drawn from the National Epidemiologic Survey on Alcohol and Related Conditions (NESARC; Wave 1, 2001–2001, n=43,093; Wave 2, 2004–2005, n=34,653). Analyses were conducted on respondents who reported current daily cigarette smoking at Wave 1 (n=6,911). Withdrawal symptoms during past quit attempts were assessed at Wave 1. Current smoking status was assessed at Wave 2. Results Wave 1 current smoking women, compared to men, were more likely to endorse any withdrawal symptoms, withdrawal-related discomfort, and withdrawal-related relapse (ps<0.0001). Women endorsed a greater number of withdrawal symptoms than men (M=2.37, SE=0.05 versus M=1.78, SE=0.04; p<0.0001). The odds of reducing and quitting smoking were significantly lower for respondents who reported any Wave 1 withdrawal symptoms, withdrawal-related discomfort, and withdrawal-related relapse. These relationships did not differ for women versus men. Among men, the odds of reducing smoking at Wave 2 decreased significantly with each cumulative withdrawal symptom compared to women (β interaction= 0.87; p=0.01). Conclusions Women were more likely to report withdrawal while the relationship between withdrawal symptoms and decreased likelihood of reducing smoking was stronger in men. Identifying gender differences in withdrawal can help develop strategies to help reduce withdrawal for both men and women. PMID:27350655

Electronic cigarette: users profile, utilization, satisfaction and perceived efficacy.

PubMed

Etter, Jean-François; Bullen, Chris

2011-11-01

To assess the profile, utilization patterns, satisfaction and perceived effects among users of electronic cigarettes ('e-cigarettes'). Internet survey in English and French in 2010. Online questionnaire. Visitors of websites and online discussion forums dedicated to e-cigarettes and to smoking cessation. There were 3587 participants (70% former tobacco smokers, 61% men, mean age 41 years). The median duration of electronic cigarette use was 3 months, users drew 120 puffs/day and used five refills/day. Almost all (97%) used e-cigarettes containing nicotine. Daily users spent $33 per month on these products. Most (96%) said the e-cigarette helped them to quit smoking or reduce their smoking (92%). Reasons for using the e-cigarette included the perception that it was less toxic than tobacco (84%), to deal with craving for tobacco (79%) and withdrawal symptoms (67%), to quit smoking or avoid relapsing (77%), because it was cheaper than smoking (57%) and to deal with situations where smoking was prohibited (39%). Most ex-smokers (79%) feared they might relapse to smoking if they stopped using the e-cigarette. Users of nicotine-containing e-cigarettes reported better relief of withdrawal and a greater effect on smoking cessation than those using non-nicotine e-cigarettes. E-cigarettes were used much as people would use nicotine replacement medications: by former smokers to avoid relapse or as an aid to cut down or quit smoking. Further research should evaluate the safety and efficacy of e-cigarettes for administration of nicotine and other substances, and for quitting and relapse prevention. © 2011 The Authors, Addiction © 2011 Society for the Study of Addiction.

Solvatochromic investigation of highly fluorescent 2-aminobithiophene derivatives.

PubMed

Bolduc, Andréanne; Dong, Yanmei; Guérin, Amélie; Skene, W G

2012-05-21

The solvatochromic and electrochemical properties of electronic push-pull 2-aminobithiophenes consisting of an aldehyde and nitro withdrawing groups were examined. With the use of an integrating sphere, the absolute quantum yields of the bithiophenes were measured. They were found to be highly fluorescent (Φfl > 70%), provided the nitro group was not located in the 4'-position. High fluorescence yields were observed regardless of solvent, except for alcohols, notably methanol and ethanol. Cryofluorescence was used to probe the bithiophene temperature dependent excited state deactivation modes. The singlet excited state deactivation mode other than fluorescence was found to be internal conversion involving rotation around the thiophene-thiophene bond. Deactivation by intersystem crossing to the triplet state occurred in ca. 40% only for the unsubstituted 2-aminobithiophene. In contrast, the fluorescence was quenched by photoinduced intramolecular electron transfer when the nitro group was located in the 4'-position of the bithiophene. Both the absorbance and fluorescence of the bithiophenes were found to be solvatochromic with more pronounced solvent dependent shifts being observed with the fluorescence. In fact, both the fluorescence and Stokes shifts were linearly dependent on the ET(30) solvent parameter. Deviations from the linear trend of the Stokes shift with ET(30) were observed in ethanol and methanol as a result of intermolecular hydrogen abstraction from the solvent and by the excited nitro group. The oxidation potential of the bithiophenes was also highly dependent on the type and number of the electron withdrawing substituents, with values ranging between 0.8 and 1.2 V vs. SCE.

29 CFR 4219.12 - Employers liable upon mass withdrawal.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 9 2010-07-01 2010-07-01 false Employers liable upon mass withdrawal. 4219.12 Section 4219... Redetermination of Withdrawal Liability Upon Mass Withdrawal § 4219.12 Employers liable upon mass withdrawal. (a... experiences successive mass withdrawals, an employer that has been determined to be liable under this subpart...

29 CFR 4219.12 - Employers liable upon mass withdrawal.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 9 2011-07-01 2011-07-01 false Employers liable upon mass withdrawal. 4219.12 Section 4219... Redetermination of Withdrawal Liability Upon Mass Withdrawal § 4219.12 Employers liable upon mass withdrawal. (a... experiences successive mass withdrawals, an employer that has been determined to be liable under this subpart...

Process for preparing 2,3-dihydroxybenzoic acid amides of tetraazaalkanes and cycloalkanes

DOEpatents

Weitl, Frederick L.; Raymond, Kenneth N.

1985-01-01

A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

Tuning anion-functionalized ionic liquids for improved SO2 capture.

PubMed

Cui, Guokai; Zheng, Junjie; Luo, Xiaoyan; Lin, Wenjun; Ding, Fang; Li, Haoran; Wang, Congmin

2013-09-27

You can have your cake and eat it too: A "dual-tuning" strategy for improving the capture of SO2 was developed by introducing electron-withdrawing sites on the anions to produce several kinds of functionalized ionic liquids. Those functionalized with a halogen group exhibited improved performance over their non-halogenated counterparts, leading to highly efficient and reversible capture. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Synthetic Approaches to TAT

DTIC Science & Technology

1990-03-30

stabilized externally by resonance stabilization of electron withdrawing substituents placed on all four Nitrogen aL,.ms (T,- N -:, ...7; 4- N -NO2 HMX, etc...or internally by ring carbonyl groups adja- cent to the ring- N -atoms (amide resonance). 1. Cyclization experiments on methylene-bisacetamide (MBA4...more, the high instability of the desired 8-membered [8]ane- N 4 system, and the difficulty to apply proper cond’tion-. what the final products can

Chemoselective N-heterocyclic carbene-catalyzed cross-benzoin reactions: importance of the fused ring in triazolium salts.

PubMed

Langdon, Steven M; Wilde, Myron M D; Thai, Karen; Gravel, Michel

2014-05-28

Morpholinone- and piperidinone-derived triazolium salts are shown to catalyze highly chemoselective cross-benzoin reactions between aliphatic and aromatic aldehydes. The reaction scope includes ortho-, meta-, and para-substituted benzaldehyde derivatives with a range of electron-donating and -withdrawing groups as well as branched and unbranched aliphatic aldehydes. Catalytic loadings as low as 5 mol % give excellent yields in these reactions (up to 99%).

Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

PubMed

Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

2015-10-26

Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of polyisoprene latex production

NASA Technical Reports Server (NTRS)

Bauman, Albert J. (Inventor)

1979-01-01

Production of high molecular weight polyisoprene latex is enhanced by administering to plants, particularly Guayule Plants, an amine containing at least one two-carbon chain substituent and preferably substituted trialkylamine of the general structure: ##STR1## where R.sub.4, R.sub.5 and R.sub.6 are alkyl, preferably ethyl and at least one of R.sub.4, R.sub.5 and R.sub.6 is preferably an electron withdrawing group substituted aryloxy or arylthio ethyl group.

Cyclometalated ruthenium(II) complexes with a bis-carbene CCC-pincer ligand.

PubMed

Zhang, You-Ming; Shao, Jiang-Yang; Yao, Chang-Jiang; Zhong, Yu-Wu

2012-08-21

The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4'-di-p-anisylamino-2,2':6',2''-terpyridine is presented. The Ru(II/III) redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.

Effects of acute alcohol withdrawal on nest building in mice selectively bred for alcohol withdrawal severity

PubMed Central

Greenberg, Gian D.; Phillips, Tamara J.; Crabbe, John C.

2017-01-01

Nest building has been used to assess thermoregulatory behavior and positive motivational states in mice. There are known genetic influences on ethanol withdrawal severity as well as individual/thermoregulatory nest building. Withdrawal Seizure-Prone (WSP-1, WSP-2) and Withdrawal Seizure-Resistant (WSR-1, WSR-2) mice were selectively bred for high vs low handling-induced convulsion (HIC) severity, respectively, during withdrawal from chronic ethanol vapor inhalation. They also differ in HIC severity during withdrawal from an acute, 4 g/kg ethanol injection. In our initial study, withdrawal from an acute dose of ethanol dose-dependently impaired nest building over the initial 24 h of withdrawal in genetically segregating Withdrawal Seizure Control (WSC) mice. In two further studies, acute ethanol withdrawal suppressed nest building for up to two days in WSP-1 females. Deficits in nest building from ethanol were limited to the initial 10 h of withdrawal in WSR-1 females and to the initial 24 h of withdrawal in WSP-1 and WSR-1 males. Effects of ethanol on nest building for up to two days were found in WSP-2 and WSR-2 mice of both sexes. Nest building deficits in female mice from the first replicate could not be explained by a general decrease in locomotor behavior. These results suggest that nest building is a novel behavioral phenotype for indexing the severity of acute ethanol withdrawal, and that genes contributing to this trait differ from those affecting acute withdrawal HIC severity. PMID:27503811

Withdrawal: Expanding a Key Addiction Construct.

PubMed

Piper, Megan E

2015-12-01

Withdrawal is an essential component of classical addiction theory; it is a vital manifestation of dependence and motivates relapse. However, the traditional conceptualization of withdrawal as a cohesive collection of symptoms that emerge during drug deprivation and decline with either the passage of time or reinstatement of drug use, may be inadequate to explain scientific findings or fit with modern theories of addiction. This article expands the current understanding of tobacco withdrawal by examining: (1) withdrawal variability; (2) underlying causes of withdrawal variability, including biological and person factors, environmental influences, and the influence of highly routinized behavioral patterns; (3) new withdrawal symptoms that allow for enhanced characterization of the withdrawal experience; and (4) withdrawal-related cognitive processes. These topics provide guidance regarding the optimal assessment of withdrawal and illustrate the potential impact modern withdrawal conceptualization and assessment could have on identifying treatment targets. © The Author 2015. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Association between lead exposure from electronic waste recycling and child temperament alterations.

PubMed

Liu, Junxiao; Xu, Xijin; Wu, Kusheng; Piao, Zhongxian; Huang, Jinrong; Guo, Yongyong; Li, Weiqiu; Zhang, Yuling; Chen, Aimin; Huo, Xia

2011-08-01

We aimed to evaluate the dose-dependent effects of lead exposure on temperament alterations in children from a primitive e-waste (obsolete electrical and electronic devices) recycling area in Guiyu of China and a control area (Chendian, China). Blood lead levels (BLL) might be correlated with temperament, health, and relevant factors that were evaluated through Parent Temperament Questionnaire (PTQ), physical examination, and residential questionnaires. We collected venipuncture blood samples from 303 children (aged 3-7 years old) between January and February 2008. Child BLL were higher in Guiyu than in Chendian (median 13.2 μg/dL, range 4.0-48.5 μg/dL vs. 8.2 μg/dL, 0-21.3 μg/dL) (P<0.01). Significant differences of mean scores in activity level (4.53±0.83 vs. 4.18±0.81), approach-withdrawal (4.62±0.85 vs. 4.31±0.89), and adaptability (4.96±0.73 vs. 4.67±0.83) were found between Guiyu and Chendian children (all P<0.01). High BLL (BLL≥10μg/dL) child had higher mean scores of approach-withdrawal when compared with those children with low BLL (BLL<10 μg/dL) (4.61±0.87 vs. 4.30±0.88, P<0.01). Location of child residence in Guiyu, and parents engagement in work related to e-waste were the risk factors related to child BLL, activity level, approach-withdrawal, adaptability, and mood. Child hand washing prior to food consumption was a protected factor for BLL and several dimensions. There are close relationships between BLL elevation, temperament alteration and the e-waste recycling activities in Guiyu. Primitive e-waste recycling may threaten the health of children by increasing BLL and altering children temperament, although the exposure to other toxicants needs to be examined in future studies. Copyright © 2011 Elsevier Inc. All rights reserved.

Comparison of the characteristics of long-term users of electronic cigarettes versus nicotine replacement therapy: A cross-sectional survey of English ex-smokers and current smokers.

PubMed

Nelson, Victoria A; Goniewicz, Maciej L; Beard, Emma; Brown, Jamie; Sheals, Kate; West, Robert; Shahab, Lion

2015-08-01

Electronic cigarettes (ECs) and nicotine replacement therapy (NRT) are non-combustible nicotine delivery devices being widely used as a partial or a complete long-term substitute for smoking. Little is known about the characteristics of long-term users, their smoking behaviour, attachment to smoking, experience of nicotine withdrawal symptoms, or their views on these devices. This study aimed to provide preliminary evidence on this and compare users of the different products. UK participants were recruited from four naturally occurring groups of long-term (≥6 months) users of either EC or NRT who had stopped or continued to smoke (N=36 per group, total N=144). Participants completed a questionnaire assessing socio-demographic and smoking characteristics, nicotine withdrawal symptoms, smoker identity and attitudes towards the products they were using. Adjusting for relevant confounders, EC use was associated with a stronger smoker identity (Wald X(2)(1)=3.9, p=0.048) and greater product endorsement (Wald X(2)(1)=4.6, p=0.024) than NRT use, irrespective of smoking status. Among ex-smokers, EC users reported less severe mood and physical symptoms (Wald X(2)(1)=6.1, p=0.014) and cravings (Wald X(2)(1)=8.5, p=0.003), higher perceived helpfulness of the product (Wald X(2)(1)=4.8, p=0.028) and lower intentions to stop using the product (Wald X(2)(1)=17.6, p<0.001) than NRT users. Compared with people who use NRT for at least 6 months, those who use EC over that time period appear to have a stronger smoker identity and like their products more. Among long-term users who have stopped smoking, ECs are perceived as more helpful than NRT, appear more effective in controlling withdrawal symptoms and continued use may be more likely. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

Estimated Withdrawals and Other Elements of Water Use in the Great Lakes Basin of the United States in 2005

USGS Publications Warehouse

Mills, Patrick C.; Sharpe, Jennifer B.

2010-01-01

Estimates of water withdrawals in the United States part of the Great Lakes Basin and 107 of its watersheds designated by the 8-digit hydrologic unit code (HUCs) indicate that about 30.3 billion gallons per day (Bgal/d) were withdrawn for practically all categories of use in 2005. Virtually all water withdrawn was freshwater. Surface-water withdrawals totaled 28.8 Bgal/d, or 95 percent of total withdrawals; about 24 Bgal/d was withdrawn from the Great Lakes or their connecting channels. Total withdrawals, and total surface-water withdrawals, decreased 7 percent from 1995 to 2005, generally following the withdrawal trends of industrial use and that of the largest use-thermoelectric power. Groundwater withdrawals increased 3 percent from 1995 to 2005 and 33 percent during 1985-2005. The substantial increase since 1985 results primarily from increases in irrigation and self-supplied domestic withdrawals. In 2005, withdrawals for public supply, domestic, and irrigation use accounted for 81 percent of groundwater withdrawals. About 21.9 Bgal/d, or 72 percent of total withdrawals for 2005, was used for thermoelectric power. Virtually all of this water was derived from surface water and used for once-through cooling at powerplants. As such, the reuse potential of this water in the basin is high, with the majority of the withdrawn water returned to its surface-water source. Public-supply withdrawals were 3.81 Bgal/d (13 percent), with withdrawals declining by about 13 percent from 1995 to 2005. In 2005, about 77 percent of the population in the Great Lakes Basin obtained drinking water from public suppliers, compared to about 78 percent in 1995 and 83 percent in 1985. Surface water consistently provided about 88 percent of the total withdrawals for public supply since 1985. Self-supplied industrial withdrawals in 2005 totaled 2.93 Bgal/d (10 percent), possibly as much as 30 percent less than in 1995. Surface water was the source for 95 percent of industrial withdrawals. Combined withdrawals for mining, irrigation, domestic, aquaculture, and livestock use (in order of decreasing rate) were 1.63 Bgal/d, or only 5 percent of total withdrawals; the withdrawals were distributed almost equally between surface-water and groundwater sources. Withdrawals for each of these uses, except livestock, increased almost continuously during 1985-2005. Withdrawals for mining increased 103 percent and for irrigation 94 percent during 1985-2005; livestock withdrawals decreased 25 percent from their peak in 1990. The number of irrigated acres increased 56 percent since 1985, totaling 750,000 acres in 2005. No use of reclaimed wastewater for industrial or irrigation applications was reported; however, sources of information regarding its use were sparse. Within the basin, the Lake Michigan watershed accounted for 15.0 Bgal/d, or 49 percent, of total water withdrawals for 2005; an estimated 12.3 Bgal/d was withdrawn directly from Lake Michigan. The State of Michigan accounted for 38 percent of total water withdrawals, representing the largest surface-water withdrawals (primarily for thermoelectric power use) and groundwater withdrawals (primarily for public supply and self-supplied domestic use). A disproportionately large percentage of surface-water withdrawals (6 percent, 1.80 Bgal/d) were in Illinois, given this state represents less than 1 percent of the land area of the basin. Ninety percent of the Illinois population served by the water withdrawn from Lake Michigan for public supply resides outside the basin. Within land-based HUCs, the Lower Maumee (04100009) of Ohio accounted for the largest total withdrawal and total surface-water withdrawal (about 0.75 Bgal/d). The St. Joseph (04050001) of Michigan and Indiana accounted for the largest total groundwater withdrawal (0.25 Bgal/d).

Drug Addiction and Its Underlying Neurobiological Basis: Neuroimaging Evidence for the Involvement of the Frontal Cortex

PubMed Central

Goldstein, Rita Z.; Volkow, Nora D.

2005-01-01

Objective Studies of the neurobiological processes underlying drug addiction primarily have focused on limbic subcortical structures. Here the authors evaluated the role of frontal cortical structures in drug addiction. Method An integrated model of drug addiction that encompasses intoxication, bingeing, withdrawal, and craving is proposed. This model and findings from neuroimaging studies on the behavioral, cognitive, and emotional processes that are at the core of drug addiction were used to analyze the involvement of frontal structures in drug addiction. Results The orbitofrontal cortex and the anterior cingulate gyrus, which are regions neuroanatomically connected with limbic structures, are the frontal cortical areas most frequently implicated in drug addiction. They are activated in addicted subjects during intoxication, craving, and bingeing, and they are deactivated during withdrawal. These regions are also involved in higher-order cognitive and motivational functions, such as the ability to track, update, and modulate the salience of a reinforcer as a function of context and expectation and the ability to control and inhibit prepotent responses. Conclusions These results imply that addiction connotes cortically regulated cognitive and emotional processes, which result in the overvaluing of drug reinforcers, the undervaluing of alternative reinforcers, and deficits in inhibitory control for drug responses. These changes in addiction, which the authors call I-RISA (impaired response inhibition and salience attribution), expand the traditional concepts of drug dependence that emphasize limbic-regulated responses to pleasure and reward. PMID:12359667

Modulation of Ethanol Withdrawal–Induced Anxiety-Like Behavior During Later Withdrawals by Treatment of Early Withdrawals With Benzodiazepine/γ-Aminobutyric Acid Ligands

PubMed Central

Knapp, Darin J.; Overstreet, David H.; Breese, George R.

2010-01-01

Background Anxiety states, including those arising during acute or protracted withdrawal periods, may be precipitating factors in alcoholic relapse. Given the cyclical nature of ethanol withdrawal associated with repeated cycles of ethanol intake and abstinence in a pattern that often spans years, meaningful attempts to model ethanol withdrawal–associated anxiety should incorporate cycled ethanol treatments. The studies reported herein examined the effects of γ-aminobutyric acid–modulating drugs on social interaction behavior—an established model of anxiety—in rats exposed to repeated cycles of ethanol treatment and withdrawal. Methods Rats were exposed to 8 to 12 g/kg/day ethanol during three 7-day dietary cycles (5 days on ethanol diet followed by 2 days on control diet). Ethanol was administered either at hour 4 of withdrawal after cessation of each of the first 2 ethanol cycles or during the final withdrawal only. In other groups, the early withdrawals were treated with alphaxalone, diazepam, PK11159, or flumazenil to block anxiety-like behavior during an untreated later (third) withdrawal. The benzodiazepine inverse agonist DMCM (methyl–6, 7–dymerhoxy–4–ethyl–beta–carboline–3–carboxylate) was also given repeatedly to determine whether it would sensitize anxiety-like behavior during a future withdrawal. Finally, the effects of all drugs on deficits in locomotor behavior were assessed. Results Pretreatment of earlier withdrawals with alphaxalone, diazepam, ethanol, or flumazenil reduced social interaction deficits during a later withdrawal, but pretreatment with PK11195 did not. In contrast, DMCM administered in lieu of early withdrawals increased social interaction deficits during an untreated later withdrawal. Locomotor deficits were significantly reversed only by the acute ethanol and diazepam treatment during the final withdrawal. Conclusions Single-dose administration of drugs that enhance or diminish activity at benzodiazepine–γ-aminobutyric acid- receptors during earlier withdrawals reduced or potentiated, respectively, anxiety-like behavior during later, drug-free withdrawals. These results support the potential of the novel strategy of using prophylactic therapy administered during early withdrawals to ameliorate symptoms of later withdrawals. PMID:15834220

Preparation and Characterization of Novel Cationic Chitosan Derivatives Bearing Quaternary Ammonium and Phosphonium Salts and Assessment of Their Antifungal Properties.

PubMed

Tan, Wenqiang; Li, Qing; Dong, Fang; Chen, Qiuhong; Guo, Zhanyong

2017-08-31

Chitosan is an abundant and renewable polysaccharide, its derivatives exhibit attractive bioactivities and the wide applications in various biomedical fields. In this paper, two novel cationic chitosan derivatives modified with quaternary phosphonium salts were successfully synthesized via trimethylation, chloride acetylation, and quaternization with tricyclohexylphosphine and triphenylphosphine. The structures and properties of synthesized products in the reactions were characterized by FTIR spectroscopy, ¹H-NMR, 31 P-NMR, elemental and thermogravimetric analysis. The antifungal activities of chitosan derivatives against four kinds of phytopathogens, including Phomopsis asparagi , Watermelon fusarium , Colletotrichum lagenarium , and Fusarium oxysporum were tested using the radial growth assay in vitro. The results revealed that the synthesized cationic chitosan derivatives showed significantly improved antifungal efficiency compared to chitosan. It was reasonably suggested that quaternary phosphonium groups enabled the obviously stronger antifungal activity of the synthesized chitosans. Especially, the triphenylphosphonium-functionalized chitosan derivative inhibited the growth of Phomopsis asparagi most effectively, with inhibitory indices of about 80% at 0.5 mg/mL. Moreover, the data demonstrated that the substituted groups with stronger electron-withdrawing ability relatively possessed greater antifungal activity. The results suggest the possibility that cationic chitosan derivatives bearing quaternary phosphonium salts could be effectively employed as novel antifungal biomaterials for application in the field of agriculture.

Highly crystalline carbon dots from fresh tomato: UV emission and quantum confinement.

PubMed

Liu, Weijian; Li, Chun; Sun, Xiaobo; Pan, Wei; Yu, Guifeng; Wang, Jinping

2017-12-01

In this article, fresh tomatoes are explored as a low-cost source to prepare high-performance carbon dots by using microwave-assisted pyrolysis. Given that amino groups might act as nucleophiles for cleaving covalent bridging ester or ether in the crosslinked macromolecules in the biomass bulk, ethylenediamine (EDA) and urea with amino groups were applied as nucleophiles to modulate the chemical composites of the carbon nanoparticles in order to tune their fluorescence emission and enhance their quantum yields. Very interestingly, the carbon dots synthesized in the presence of urea had a highly crystalline nature, a low-degree amorphous surface and were smaller than 5 nm. Moreover, the doped N contributed to the formation of a cyclic form of core that resulted in a strong electron-withdrawing ability within the conjugated C plane. Therefore, this type of carbon dot exhibited marked quantum confinement, with the maximum fluorescence peak located in the UV region. Carbon nanoparticles greater than 20 nm in size, prepared using pristine fresh tomato and in the presence of EDA, emitted surface state controlled fluorescence. Additionally, carbon nanoparticles synthesized using fresh tomato pulp in the presence of EDA and urea were explored for bioimaging of plant pathogenic fungi and the detection of vanillin.

Highly crystalline carbon dots from fresh tomato: UV emission and quantum confinement

NASA Astrophysics Data System (ADS)

Liu, Weijian; Li, Chun; Sun, Xiaobo; Pan, Wei; Yu, Guifeng; Wang, Jinping

2017-12-01

In this article, fresh tomatoes are explored as a low-cost source to prepare high-performance carbon dots by using microwave-assisted pyrolysis. Given that amino groups might act as nucleophiles for cleaving covalent bridging ester or ether in the crosslinked macromolecules in the biomass bulk, ethylenediamine (EDA) and urea with amino groups were applied as nucleophiles to modulate the chemical composites of the carbon nanoparticles in order to tune their fluorescence emission and enhance their quantum yields. Very interestingly, the carbon dots synthesized in the presence of urea had a highly crystalline nature, a low-degree amorphous surface and were smaller than 5 nm. Moreover, the doped N contributed to the formation of a cyclic form of core that resulted in a strong electron-withdrawing ability within the conjugated C plane. Therefore, this type of carbon dot exhibited marked quantum confinement, with the maximum fluorescence peak located in the UV region. Carbon nanoparticles greater than 20 nm in size, prepared using pristine fresh tomato and in the presence of EDA, emitted surface state controlled fluorescence. Additionally, carbon nanoparticles synthesized using fresh tomato pulp in the presence of EDA and urea were explored for bioimaging of plant pathogenic fungi and the detection of vanillin.

Can nitro groups really anchor onto TiO 2? Case study of dye-to-TiO 2 adsorption using azo dyes with NO 2 substituents

DOE PAGES

Zhang, Lei; Cole, Jacqueline M.

2016-06-21

The nitro group has recently been suggested as a new type of anchor for dye-sensitized solar cells (DSSCs) and has shown promising optoelectronic properties. Considering the excellent electron withdrawing ability of the nitro group and wider materials selection brought about by this substituent, it is helpful to evaluate the interfacial structures and photophysics of more organic dyes where NO 2 poses as the dye-to-TiO 2 anchor. A computational study on a family of azo dyes bearing a nitro group is presented in this paper, where the effect of certain side groups on their optical properties is examined. Both isolated dyemore » molecules and dye/TiO 2 nanocomposites are studied via density functional theory and time-dependent density functional theory, with complementary experimental UV/vis absorption spectroscopy and photovoltaic device testing. Results demonstrate that these nitro-containing dyes prefer a monodentate anchoring mode on a TiO 2 cluster. These nitro dyes reveal weak, but non-negligible, adsorption onto TiO 2; yet, very low photovoltaic performance once incorporated into a DSSC device. Finally, this poor delivery of nitro groups as DSSC anchors is ostensibly inconsistent with previous findings; but is rationalized via the “auxiliary anchor” concept.« less

Effects of acute alcohol withdrawal on nest building in mice selectively bred for alcohol withdrawal severity.

PubMed

Greenberg, Gian D; Phillips, Tamara J; Crabbe, John C

2016-10-15

Nest building has been used to assess thermoregulatory behavior and positive motivational states in mice. There are known genetic influences on ethanol withdrawal severity as well as individual/thermoregulatory nest building. Withdrawal Seizure-Prone (WSP-1, WSP-2) and Withdrawal Seizure-Resistant (WSR-1, WSR-2) mice were selectively bred for high vs low handling-induced convulsion (HIC) severity, respectively, during withdrawal from chronic ethanol vapor inhalation. They also differ in HIC severity during withdrawal from an acute, 4g/kg ethanol injection. In our initial study, withdrawal from an acute dose of ethanol dose-dependently impaired nest building over the initial 24h of withdrawal in genetically segregating Withdrawal Seizure Control (WSC) mice. In two further studies, acute ethanol withdrawal suppressed nest building for up to two days in WSP-1 females. Deficits in nest building from ethanol were limited to the initial 10h of withdrawal in WSR-1 females and to the initial 24h of withdrawal in WSP-1 and WSR-1 males. Effects of ethanol on nest building for up to two days were found in WSP-2 and WSR-2 mice of both sexes. Nest building deficits in female mice from the first replicate could not be explained by a general decrease in locomotor behavior. These results suggest that nest building is a novel behavioral phenotype for indexing the severity of acute ethanol withdrawal, and that genes contributing to this trait differ from those affecting acute withdrawal HIC severity. Published by Elsevier Inc.

SSRI and SNRI withdrawal symptoms reported on an internet forum.

PubMed

Stockmann, Tom; Odegbaro, Dolapo; Timimi, Sami; Moncrieff, Joanna

2018-05-09

Antidepressant withdrawal symptoms are well-recognised, but their potential duration remains uncertain. We aimed to describe the characteristics of withdrawal associated with two popular classes of antidepressants, including duration. We analysed the content of a sample of posts on an antidepressant withdrawal website. We compared the characteristics of withdrawal associated with SSRIs and SNRIs, including time of onset, duration and nature of symptoms. 110 posts about SSRI withdrawal, and 63 concerning SNRI withdrawal, were analysed. The mean duration of withdrawal symptoms was significantly longer with SSRIs than SNRIs: 90.5 weeks (standard deviation, SD, 150.0) and 50.8 weeks (SD 76.0) respectively; p = 0.043). Neurological symptoms, such as 'brain zaps,' were more common among SNRI users (p = 0.023). Psychosexual/genitourinary symptoms may be more common among SSRI users (p = 0.054). The website aims to help people with antidepressant withdrawal, and is therefore likely to attract people who have difficulties. Length of prior use of antidepressants was long, with a mean of 252.2 weeks (SD 250.8). People accessing antidepressant withdrawal websites report experiencing protracted withdrawal symptoms. There are some differences in the characteristics of withdrawal associated with different classes of antidepressants.

Reconstruction of global gridded monthly sectoral water withdrawals for 1971-2010 and analysis of their spatiotemporal patterns

NASA Astrophysics Data System (ADS)

Huang, Zhongwei; Hejazi, Mohamad; Li, Xinya; Tang, Qiuhong; Vernon, Chris; Leng, Guoyong; Liu, Yaling; Döll, Petra; Eisner, Stephanie; Gerten, Dieter; Hanasaki, Naota; Wada, Yoshihide

2018-04-01

Human water withdrawal has increasingly altered the global water cycle in past decades, yet our understanding of its driving forces and patterns is limited. Reported historical estimates of sectoral water withdrawals are often sparse and incomplete, mainly restricted to water withdrawal estimates available at annual and country scales, due to a lack of observations at seasonal and local scales. In this study, through collecting and consolidating various sources of reported data and developing spatial and temporal statistical downscaling algorithms, we reconstruct a global monthly gridded (0.5°) sectoral water withdrawal dataset for the period 1971-2010, which distinguishes six water use sectors, i.e., irrigation, domestic, electricity generation (cooling of thermal power plants), livestock, mining, and manufacturing. Based on the reconstructed dataset, the spatial and temporal patterns of historical water withdrawal are analyzed. Results show that total global water withdrawal has increased significantly during 1971-2010, mainly driven by the increase in irrigation water withdrawal. Regions with high water withdrawal are those densely populated or with large irrigated cropland production, e.g., the United States (US), eastern China, India, and Europe. Seasonally, irrigation water withdrawal in summer for the major crops contributes a large percentage of total annual irrigation water withdrawal in mid- and high-latitude regions, and the dominant season of irrigation water withdrawal is also different across regions. Domestic water withdrawal is mostly characterized by a summer peak, while water withdrawal for electricity generation has a winter peak in high-latitude regions and a summer peak in low-latitude regions. Despite the overall increasing trend, irrigation in the western US and domestic water withdrawal in western Europe exhibit a decreasing trend. Our results highlight the distinct spatial pattern of human water use by sectors at the seasonal and annual timescales. The reconstructed gridded water withdrawal dataset is open access, and can be used for examining issues related to water withdrawals at fine spatial, temporal, and sectoral scales.

Synthesis, characterization and nonlinear optical properties of symmetrically substituted dibenzylideneacetone derivatives

NASA Astrophysics Data System (ADS)

Sunil Kumar Reddy, N.; Badam, Rajashekar; Sattibabu, Romala; Molli, Muralikrishna; Sai Muthukumar, V.; Siva Sankara Sai, S.; Rao, G. Nageswara

2014-11-01

We report here the nonlinear optical (NLO) properties of eight bis-chalcones of D-π-A-π-D type. These dibenzylideneacetone (DBA) derivatives are synthesized by Claisen-Schmidt reaction. The compounds are characterized by UV-vis, FTIR, 1H NMR, 13C NMR, mass spectroscopy and powder XRD. By substituting different groups (electron withdrawing and electron donating) at 'para' and 'meta' positions of the aromatic ring, we observed an enhancement in second harmonic generation with substitution at 'para' position. These compounds have also showed higher two-photon absorption compared to other chalcones reported in literature. These compounds, exhibiting both second and third order NLO effects, are plausible candidate materials in photonic devices.

The effect of triiodothyronine on maturation and differentiation of oligodendrocyte progenitor cells during remyelination following induced demyelination in male albino rat.

PubMed

El-Tahry, H; Marei, H; Shams, A; El-Shahat, M; Abdelaziz, H; Abd El-Kader, M

2016-06-01

Demyelination was induced by two weeks cuprizone treatment. Rats of +ve control and triiodothyronine (T3) then received three subcutaneous injections of either saline or T3 day after day and sacrificed at the end of the third and fifth weeks. Animals in -ve control group received only standard rodent chow. After one week of cuprizone withdrawal the corpus callosum in +ve control and T3 treated rats was still demyelinated as revealed by MBP immunohistochemistry. The assay of PLP gene showed significant increase of T3 treated group compared to both the -ve control and +ve control groups. After three weeks, significant improvement in myelination was detected in T3-treated group compared to +ve control as detected by both MBP immunohistochemistry and electron microscopy. After one week of cuprizone withdrawal, PDGFRα positive cells and gene expression showed significant increase in +ve control and T3-treated groups as compared to -ve control with insignificant difference in between the former two groups. After three weeks of cuprizone withdrawal, PDGFRα positive cells in T3-treated and +ve control groups decreased to the control levels. These results suggest that T3 was effective in improving remyelination when administered during acute phase and might direct progenitor lineage toward oligodendrocytes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Time-course of the DSM-5 cannabis withdrawal symptoms in poly-substance abusers

PubMed Central

2013-01-01

Background Evidence is accumulating that a cannabis withdrawal syndrome is common, of clinical significance, and has a clear time course. Up till now, very limited data exist on the cannabis withdrawal symptoms in patients with co-morbid substance use disorders, other than cannabis use and tobacco use. Methods Symptoms of withdrawal were assessed through patient self-reports during detoxification in Danish residential rehabilitation centers. Patients (n = 90) completed booklets three times during their first month at the treatment centre. Self-reported withdrawal symptoms was rated using the DSM-5 Withdrawal Symptom Check List with withdrawal symptoms from all classes of substances, with no indication that the described symptoms should be attributed to withdrawal. Self-reported time since last use of cannabis was used as a predictor of cannabis withdrawal severity. Results With the exception of loss of appetite, time since last use of cannabis was associated with all types of withdrawal symptoms listed in the DSM-5. Only four of 19 symptoms intended to measure withdrawal from other substances were related to time since last use of cannabis, including vivid, unpleasant dreams. Conclusions The findings yield strong support to the notion of a cannabis withdrawal syndrome, and gives further evidence for the inclusion of the criterion of vivid, unpleasant dreams. Further, the findings speak against the significance of demand characteristics in determining the course of the symptoms of cannabis withdrawal. PMID:24118963

The Hammett relationship and reactions in the excited electronic state: hemithioindigo Z/E-photoisomerization.

PubMed

Cordes, Thorben; Schadendorf, Torsten; Priewisch, Beate; Rück-Braun, Karola; Zinth, Wolfgang

2008-01-31

The photochemical reaction dynamics of a set of photochromic compounds based on thioindigo and stilbene molecular parts (hemithioindigos, HTI) are presented. Photochemical Z/E isomerization around the central double bond occurs with time constants of 216 ps (Z --> E) and 10 ps (E --> Z) for a 5-methyl-hemithioindigo. Chemical substitution on the stilbene moiety causes unusually strong changes in the reaction rate. Electron-donating substituents in the position para to the central double bond (e.g., para-methoxy) strongly accelerate the reaction, while the reaction is drastically slowed by electron-withdrawing groups in this position (e.g., para-nitrile). We correlate the experimental data of seven HTI-compounds in a quantitative manner using the Hammett equation and present a qualitative explanation for the application of ground-state Hammett constants to describe the photoisomerization reaction.

A new look into conformational, vibrational and electronic structure analysis of 3,4-dimethoxybenzonitrile.

PubMed

Arjunan, V; Devi, L; Remya, P; Mohan, S

2013-09-01

The FTIR and FT-Raman spectra of 3,4-dimethoxybenzonitrile (34DMBN) have been analysed. Quantum chemical studies were performed with B3LYP method using 6-311++G(d,p), 6-31G(d,p) and cc-pVTZ basis sets. The electron donating effect of -OCH3 and electron withdrawing effect of -C≡N groups on the ring parameters were thoroughly analysed. The structural parameters, energies, thermodynamic properties, vibrational frequencies and the NBO charges of 34DMBN were determined. The (1)H and (13)C chemical shifts with respect to TMS were investigated and also calculated theoretically using the gauge independent atomic orbital method and compared with the experimental data. The delocalisation energy of different types of bonding interactions was investigated. Copyright © 2013 Elsevier B.V. All rights reserved.

Solution-Processable Balanced Ambipolar Field-Effect Transistors Based on Carbonyl-Regulated Copolymers.

PubMed

Yang, Chengdong; Fang, Renren; Yang, Xiongfa; Chen, Ru; Gao, Jianhua; Fan, Hanghong; Li, Hongxiang; Hu, Wenping

2018-04-04

It is very important to develop ambipolar field effect transistors to construct complementary circuits. To obtain balanced hole- and electron-transport properties, one of the key issues is to regulate the energy levels of the frontier orbitals of the semiconductor materials by structural tailoring, so that they match well with the electrode Fermi levels. Five conjugated copolymers were synthesized and exhibited low LUMO energy levels and narrow bandgaps on account of the strong electron-withdrawing effect of the carbonyl groups. Polymer thin film transistors were prepared by using a solution method and exhibited high and balanced hole and electron mobility of up to 0.46 cm 2  V -1  s -1 , which suggested that these copolymers are promising ambipolar semiconductor materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-molecular diodes based on opioid derivatives.

PubMed

Siqueira, M R S; Corrêa, S M; Gester, R M; Del Nero, J; Neto, A M J C

2015-12-01

We propose an efficient single-molecule rectifier based on a derivative of opioid. Electron transport properties are investigated within the non-equilibrium Green's function formalism combined with density functional theory. The analysis of the current-voltage characteristics indicates obvious diode-like behavior. While heroin presents rectification coefficient R>1, indicating preferential electronic current from electron-donating to electron-withdrawing, 3 and 6-acetylmorphine and morphine exhibit contrary behavior, R<1. Our calculations indicate that the simple inclusion of acetyl groups modulate a range of devices, which varies from simple rectifying to resonant-tunneling diodes. In particular, the rectification rations for heroin diodes show microampere electron current with a maximum of rectification (R=9.1) at very low bias voltage of ∼0.6 V and (R=14.3)∼1.8 V with resistance varying between 0.4 and 1.5 M Ω. Once most of the current single-molecule diodes usually rectifies in nanoampere, are not stable over 1.0 V and present electrical resistance around 10 M. Molecular devices based on opioid derivatives are promising in molecular electronics.

DFT/TDDFT investigation on the photophysical properties of a series of phosphorescent cyclometalated complexes based on the benchmark complex FIrpic

NASA Astrophysics Data System (ADS)

Han, Deming; Gong, Ping; Lv, Shuhui; Zhao, Lihui; Zhao, Henan

2018-05-01

The photophysical properties of four Ir(III) complexes have been investigated by means of the density functional theory/time-dependent density functional theory (DFT/TDDFT). The effect of the electron-withdrawing and electron-donating substituents on charge injection, transport, absorption and phosphorescent properties has been studied. The theoretical calculation shows that the lowest-lying singlet absorptions for complexes 1-4 are located at 387, 385, 418 and 386 nm, respectively. For 1-4, the phosphorescence at 465, 485, 494 and 478 nm is mainly attributed to the LUMO → HOMO and LUMO → HOMO-1 transition configurations characteristics. In addition, ionisation potential (IP), electron affinities (EAs) and reorganisation energy have been investigated to evaluate the charge transfer and balance properties between hole and electron. The balance of the reorganisation energies for complex 3 is better than others. The difference between hole transport and electron transport for complex 3 is the smallest among these complexes, which is beneficial to achieve the hole and electron transfer balance in emitting layer.

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

NASA Technical Reports Server (NTRS)

Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

2002-01-01

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

[An examination of the determinants of social withdrawal and affinity for social withdrawal].

PubMed

Watanabe, Asami; Matsui, Yutaka; Takatsuka, Yusuke

2010-12-01

This study examined the determinants of social withdrawal using data from a survey by the Tokyo Metropolitan Government Office for Youth Affairs and Public Safety (2008). In addition, this study identified young people who showed an affinity for social withdrawal although they were not in a state of withdrawal, and examined the determinants of an affinity for social withdrawal. The results of stepwise discriminant analysis showed that factors such as social phobia, depression, violence, and emotional bonds with family differentiated between the general youth group and the social withdrawal group and the "affinity group". Social phobia, violence, and refusal to be interfered in self-decision making differentiated between the social withdrawal group and the "affinity group". This study shows that an "affinity group" should be cared as well as an actual withdrawal group.

20 CFR 408.355 - Can you withdraw your application?

Code of Federal Regulations, 2010 CFR

2010-04-01

... Section 408.355 Employees' Benefits SOCIAL SECURITY ADMINISTRATION SPECIAL BENEFITS FOR CERTAIN WORLD WAR II VETERANS Filing Applications Withdrawal of Application § 408.355 Can you withdraw your application? (a) Request for withdrawal filed before a determination is made. You may withdraw your application...

"Is That A Method of Birth Control?" A Qualitative Exploration of Young Women's Use of Withdrawal.

PubMed

Arteaga, Stephanie; Gomez, Anu Manchikanti

2016-01-01

Despite its ubiquity, withdrawal is understudied as a family planning method. We investigated the context of and decision making around withdrawal use, drawing on in-depth, qualitative interviews with 38 Black and Latina women (ages 18 to 24). We examined contraceptive use histories to understand when and why participants used withdrawal. The majority of participants (n = 29; 76%) had used withdrawal in their lifetimes, though two-thirds of users mentioned withdrawal in their contraceptive histories only after interviewer prompts. Withdrawal was primarily used during transitions between contraceptive methods and when other methods were not desired. Relationship context was also an important factor, as many used withdrawal to increase intimacy with their partners; because they felt condoms were no longer necessary due to monogamy; or to fulfill their partners' preferences to increase sexual pleasure. Our findings indicate that decision making around withdrawal is embedded in situational and relational contexts. Future research should explore how health care providers and sex educators can engage young women in discussions of withdrawal's benefits and constraints. A harm reduction framework, which recognizes that optimal use of withdrawal is preferable to not using a pregnancy prevention method at all, may inform the ways that withdrawal can be addressed in clinical and educational settings.

Ultrasensitive near-infrared fluorescence-enhanced probe for in vivo nitroreductase imaging.

PubMed

Li, Yuhao; Sun, Yun; Li, Jiachang; Su, Qianqian; Yuan, Wei; Dai, Yu; Han, Chunmiao; Wang, Qiuhong; Feng, Wei; Li, Fuyou

2015-05-20

Nitroreductase (NTR) can be overexpressed in hypoxic tumors, thus the selective and efficient detection of NTR is of great importance. To date, although a few optical methods have been reported for the detection of NTR in solution, an effective optical probe for NTR monitoring in vivo is still lacking. Therefore, it is necessary to develop a near-infrared (NIR) fluorescent detection probe for NTR. In this study, five NIR cyanine dyes with fluorescence reporting structure decorated with different nitro aromatic groups, Cy7-1-5, have been designed and explored for possible rapid detection of NTR. Our experimental results presented that only a para-nitro benzoate group modified cyanine probe (Cy7-1) could serve as a rapid NIR fluorescence-enhanced probe for monitoring and bioimaging of NTR. The structure-function relationship has been revealed by theoretical study. The linker connecting the detecting and fluorescence reporting groups and the nitro group position is a key factor for the formation of hydrogen bonds and spatial structure match, inducing the NTR catalytic ability enhancement. The in vitro response and mechanism of the enzyme-catalyzed reduction of Cy7-1 have been investigated through kinetic optical studies and other methods. The results have indicated that an electro-withdrawing group induced electron-transfer process becomes blocked when Cy7-1 is catalytically reduced to Cy7-NH2 by NTR, which is manifested in enhanced fluorescence intensity during the detection process. Confocal fluorescence imaging of hypoxic A549 cells has confirmed the NTR detection ability of Cy7-1 at the cellular level. Importantly, Cy7-1 can detect tumor hypoxia in a murine hypoxic tumor model, showing a rapid and significant enhancement of its NIR fluorescence characteristics suitable for fluorescence bioimaging. This method may potentially be used for tumor hypoxia diagnosis.

Catalytic trimerization of aromatic nitriles for synthesis of polyimide matrix resins

NASA Technical Reports Server (NTRS)

Hsu, L. C.

1974-01-01

Aromatic nitriles may be trimerized at moderate temperature and pressure with p-toluenesulfonic acid as catalyst. Studies were conducted to establish the effect of the reaction temperature, pressure, time, and catalyst concentration on yield of the trimerized product. Trimerization studies were also conducted to establish the effect of substituting electron donating or withdrawing groups on benzonitrile. Preliminary results of using the catalytic trimerization approach to prepare s-triazine cross-linked polyimide/graphite fiber composites are presented.

Effects of Acute Withdrawal on Ethanol-Induced Conditioned Place Preference in DBA/2J mice

PubMed Central

Dreumont, Sarah E.; Cunningham, Christopher L.

2013-01-01

Rationale Re-exposure to ethanol during acute withdrawal might facilitate the transition to alcoholism by enhancing the rewarding effect of ethanol. Objective The conditioned place preference (CPP) procedure was used to test whether ethanol reward is enhanced during acute withdrawal. Methods DBA/2J mice were exposed to an unbiased one-compartment CPP procedure. Ethanol (0.75, 1.0 or 1.5 g/kg IP) was paired with a distinctive floor cue (CS+), whereas saline was paired with a different floor cue (CS−). The Withdrawal (W) group received CS+ trials during acute withdrawal produced by a large dose of ethanol (4 g/kg) given 8 h before each trial. The No Withdrawal (NW) group did not experience acute withdrawal during conditioning trials, but was matched for acute withdrawal experience. Floor preference was tested in the absence of ethanol or acute withdrawal. Results All groups eventually showed a dose-dependent preference for the ethanol-paired cue, but development of CPP was generally more rapid and stable in the W groups than in the NW groups. Acute withdrawal suppressed the normal activating effect of ethanol during CS+ trials, but there were no group differences in test activity. Conclusions Acute withdrawal enhanced ethanol’s rewarding effect as indexed by CPP. Since this effect depended on ethanol exposure during acute withdrawal, the enhancement of ethanol reward was likely mediated by the alleviation of acute withdrawal, i.e., negative reinforcement. Enhancement of ethanol reward during acute withdrawal may be a key component in the shift from episodic to chronic ethanol consumption that characterizes alcoholism. PMID:24096534

A genetic perspective on the proposed inclusion of cannabis withdrawal in DSM-5.

PubMed

Verweij, K J H; Agrawal, A; Nat, N O; Creemers, H E; Huizink, A C; Martin, N G; Lynskey, M T

2013-08-01

Various studies support the inclusion of cannabis withdrawal in the diagnosis of cannabis use disorder (CUD) in the upcoming DSM-5. The aims of the current study were to (1) estimate the prevalence of DSM-5 cannabis withdrawal (criterion B), (2) estimate the role of genetic and environmental influences on individual differences in cannabis withdrawal and (3) determine the extent to which genetic and environmental influences on cannabis withdrawal overlap with those on DSM-IV-defined abuse/dependence. The sample included 2276 lifetime cannabis-using adult Australian twins. Cannabis withdrawal was defined in accordance with criterion B of the proposed DSM-5 revisions. Cannabis abuse/dependence was defined as endorsing one or more DSM-IV criteria of abuse or three or more dependence criteria. The classical twin model was used to estimate the genetic and environmental influences on variation in cannabis withdrawal, along with its covariation with abuse/dependence. Of all the cannabis users, 11.9% met criteria for cannabis withdrawal. Around 50% of between-individual variation in withdrawal could be attributed to additive genetic variation, and the rest of the variation was mostly due to non-shared environmental influences. Importantly, the genetic influences on cannabis withdrawal almost completely (99%) overlapped with those on abuse/dependence. We have shown that cannabis withdrawal symptoms exist among cannabis users, and that cannabis withdrawal is moderately heritable. Genetic influences on cannabis withdrawal are the same as those affecting abuse/dependence. These results add to the wealth of literature that recommends the addition of cannabis withdrawal to the diagnosis of DSM-5 CUD.

Worldwide withdrawal of medicinal products because of adverse drug reactions: a systematic review and analysis.

PubMed

Onakpoya, Igho J; Heneghan, Carl J; Aronson, Jeffrey K

2016-07-01

We have systematically identified medicinal products withdrawn worldwide because of adverse drug reactions, assessed the level of evidence used for making the withdrawal decisions, and explored the patterns of withdrawals over time. We searched PubMed, the WHO database of withdrawn products, and selected texts. We included products that were withdrawn after launch from 1950 onwards, excluding non-human and over-the-counter medicines. We assessed the levels of evidence on which withdrawals were based using the Oxford Center for Evidence Based Medicine Levels of Evidence. Of 353 medicinal products withdrawn from any country, only 40 were withdrawn worldwide. Anecdotal reports were cited as evidence for withdrawal in 30 (75%) and deaths occurred in 27 (68%). Hepatic, cardiac, and nervous system toxicity accounted for over 60% of withdrawals. In 28 cases, the first withdrawal was initiated by the manufacturer. The median interval between the first report of an adverse drug reaction that led to withdrawal and the first withdrawal was 1 year (range 0-43 years). Worldwide withdrawals occurred within 1 year after the first withdrawal in any country. In conclusion, the time it takes for drugs to be withdrawn worldwide after reports of adverse drug reactions has shortened over time. However, there are inconsistencies in current withdrawal procedures when adverse drug reactions are suspected. A uniform method for establishing worldwide withdrawal of approved medicinal products when adverse drug reactions are suspected should be developed, to facilitate global withdrawals. Rapid synthesis of the evidence on harms should be a priority when serious adverse reactions are suspected.

A genetic perspective on the proposed inclusion of cannabis withdrawal in the DSM-5

PubMed Central

Verweij, K.J.H.; Agrawal, A.; Nat, N.O.; Creemers, H.E.; Huizink, A.C.; Martin, N.G.; Lynskey, M.T.

2013-01-01

Background Various studies support the inclusion of cannabis withdrawal to the diagnosis of cannabis use disorders in the upcoming DSM-5. The aims of the current study were to (1) estimate the prevalence of DSM-5 cannabis withdrawal (Criterion B), (2) estimate the role of genetic and environmental influences on individual differences in cannabis withdrawal, and (3) determine the extent to which genetic and environmental influences on cannabis withdrawal overlap with those on DSM-IV defined abuse/dependence. Methods The sample included 2276 lifetime cannabis-using adult Australian twins. Cannabis withdrawal was defined in accordance with Criterion B of the proposed DSM-5 revisions. Cannabis abuse/dependence was defined as endorsing one or more DSM-IV criteria of abuse or three or more dependence criteria. The classical twin model was used to estimate the genetic and environmental influences on variation in cannabis withdrawal, as well as its covariation with abuse/dependence. Results Of all cannabis users 11.9% met criteria for cannabis withdrawal. Around 50% of between-individual variation in withdrawal could be attributed to additive genetic variation, and the rest of the variation was mostly due to non-shared environmental influences. Importantly, the genetic influences on cannabis withdrawal almost completely (99%) overlapped with those on abuse/dependence. Conclusions We showed that cannabis withdrawal symptoms exist among cannabis users, and that cannabis withdrawal is moderately heritable. Genetic influences on cannabis withdrawal are the same as those influencing abuse/dependence. These results add to the wealth of literature that recommends the addition of cannabis withdrawal to the diagnosis of DSM-5 cannabis use disorders. PMID:23194657

Evaluation of the safety profile of an electronic vapour product used for two years by smokers in a real-life setting.

PubMed

Walele, Tanvir; Bush, Jim; Koch, Annelize; Savioz, Rebecca; Martin, Claire; O'Connell, Grant

2018-02-01

The safety profile of Puritane™, a closed system electronic vapour product (EVP), was evaluated when used by smokers of conventional cigarettes (CCs) for 24 months in a real-life setting. The study was a two-centre ambulatory clinical study with 209 healthy volunteers. Outcome measures included adverse events (AEs), vital signs, electrocardiogram, lung function tests, exposure to nicotine and selected smoke constituents, nicotine withdrawal effects and smoking desire. No serious AEs related to EVP use were observed. The most frequently reported AEs were headache, nasopharyngitis, sore throat and cough, reported by 28.7%, 28.7%, 19.6% and 16.7% of subjects, respectively, which dissipated over time. Small decreases in lung function were not considered clinically relevant. No clinically relevant findings were observed in the other safety parameters. From Month 2, nicotine withdrawal symptoms decreased. Smoking desire and CC consumption steadily decreased over time in all subjects. EVP use was associated with reduced exposure to cigarette smoke constituents, whereas urinary nicotine levels remained close to baseline. Body weight did not increase in CC subjects switching to the EVP. In conclusion, the aerosol of the EVP at study was well tolerated and not associated with any clinically relevant health concerns after usage for up to 24 months. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

40 CFR 74.18 - Withdrawal.

Code of Federal Regulations, 2014 CFR

2014-07-01

... opt-in source may request to withdraw from the Acid Rain Program by submitting an administrative... paragraph (f)(1) of this section. (b) Requesting withdrawal. To withdraw from the Acid Rain Program, the...-in source's prior violations. An opt-in source that withdraws from the Acid Rain Program shall comply...

40 CFR 74.18 - Withdrawal.

Code of Federal Regulations, 2013 CFR

2013-07-01

... opt-in source may request to withdraw from the Acid Rain Program by submitting an administrative... paragraph (f)(1) of this section. (b) Requesting withdrawal. To withdraw from the Acid Rain Program, the...-in source's prior violations. An opt-in source that withdraws from the Acid Rain Program shall comply...

40 CFR 74.18 - Withdrawal.

Code of Federal Regulations, 2012 CFR

2012-07-01

... opt-in source may request to withdraw from the Acid Rain Program by submitting an administrative... paragraph (f)(1) of this section. (b) Requesting withdrawal. To withdraw from the Acid Rain Program, the...-in source's prior violations. An opt-in source that withdraws from the Acid Rain Program shall comply...

40 CFR 74.18 - Withdrawal.

Code of Federal Regulations, 2011 CFR

2011-07-01

... opt-in source may request to withdraw from the Acid Rain Program by submitting an administrative... paragraph (f)(1) of this section. (b) Requesting withdrawal. To withdraw from the Acid Rain Program, the...-in source's prior violations. An opt-in source that withdraws from the Acid Rain Program shall comply...

40 CFR 74.18 - Withdrawal.

Code of Federal Regulations, 2010 CFR

2010-07-01

... opt-in source may request to withdraw from the Acid Rain Program by submitting an administrative... paragraph (f)(1) of this section. (b) Requesting withdrawal. To withdraw from the Acid Rain Program, the...-in source's prior violations. An opt-in source that withdraws from the Acid Rain Program shall comply...

Estimated Use of Water in the United States in 2000

USGS Publications Warehouse

Hutson, Susan S.; Barber, Nancy L.; Kenny, Joan F.; Linsey, Kristin S.; Lumia, Deborah S.; Maupin, Molly A.

2004-01-01

Estimates of water use in the United States indicate that about 408 billion gallons per day (one thousand million gallons per day, abbreviated Bgal/d) were withdrawn for all uses during 2000. This total has varied less than 3 percent since 1985 as withdrawals have stabilized for the two largest uses?thermoelectric power and irrigation. Fresh ground-water withdrawals (83.3 Bgal/d) during 2000 were 14 percent more than during 1985. Fresh surface-water withdrawals for 2000 were 262 Bgal/d, varying less than 2 percent since 1985. About 195 Bgal/d, or 48 percent of all freshwater and saline-water withdrawals for 2000, were used for thermoelectric power. Most of this water was derived from surface water and used for once-through cooling at power plants. About 52 percent of fresh surface-water withdrawals and about 96 percent of saline-water withdrawals were for thermoelectric-power use. Withdrawals for thermoelectric power have been relatively stable since 1985. Irrigation remained the largest use of freshwater in the United States and totaled 137 Bgal/d for 2000. Since 1950, irrigation has accounted for about 65 percent of total water withdrawals, excluding those for thermoelectric power. Historically, more surface water than ground water has been used for irrigation. However, the percentage of total irrigation withdrawals from ground water has continued to increase, from 23 percent in 1950 to 42 percent in 2000. Total irrigation withdrawals were 2 percent more for 2000 than for 1995, because of a 16-percent increase in ground-water withdrawals and a small decrease in surface-water withdrawals. Irrigated acreage more than doubled between 1950 and 1980, then remained constant before increasing nearly 7 percent between 1995 and 2000. The number of acres irrigated with sprinkler and microirrigation systems has continued to increase and now comprises more than one-half the total irrigated acreage. Public-supply withdrawals were more than 43 Bgal/d for 2000. Public-supply withdrawals during 1950 were 14 Bgal/d. During 2000, about 85 percent of the population in the United States obtained drinking water from public suppliers, compared to 62 percent during 1950. Surface water provided 63 percent of the total during 2000, whereas surface water provided 74 percent during 1950. Self-supplied industrial withdrawals totaled nearly 20 Bgal/d in 2000, or 12 percent less than in 1995. Compared to 1985, industrial self-supplied withdrawals declined by 24 percent. Estimates of industrial water use in the United States were largest during the years from 1965 to 1980, but during 2000, estimates were at the lowest level since reporting began in 1950. Combined withdrawals for self-supplied domestic, livestock, aquaculture, and mining were less than 13 Bgal/d for 2000, and represented about 3 percent of total withdrawals. California, Texas, and Florida accounted for one-fourth of all water withdrawals for 2000. States with the largest surface-water withdrawals were California, which had large withdrawals for irrigation and thermoelectric power, and Texas, which had large withdrawals for thermoelectric power. States with the largest ground-water withdrawals were California, Texas, and Nebraska, all of which had large withdrawals for irrigation.

Can Diastat Grafts Meet the Challenges of Daily Punctures?

PubMed

Chandran, Prem K G; Messer, Diane; Sidwell, Richard A; Stubbs, David H; Nish, Andrew D

1997-01-01

To determine whether Diastat grafts can meet the challenges of daily needle punctures required for home hemodialysis (HD), a retrospective analysis was performed on the experience with 47 grafts placed in 44 patients receiving HD three times a week. The control group consisted of 17 patients who received 17 stretch polytetrafluoroethylene (s-PTFE) grafts. Apart from their ability to better contain bleeding after needle withdrawal, in all measures of longevity the Diastat grafts were outperformed by the s-PTFE grafts. No more direct data exist to address the original challenge.

8 CFR 235.4 - Withdrawal of application for admission.

Code of Federal Regulations, 2010 CFR

2010-01-01

... right to withdraw his or her application for admission. Permission to withdraw an application for... 8 Aliens and Nationality 1 2010-01-01 2010-01-01 false Withdrawal of application for admission... INSPECTION OF PERSONS APPLYING FOR ADMISSION § 235.4 Withdrawal of application for admission. The Attorney...

Groundwater withdrawals and associated well descriptions for the Nevada National Security Site, Nye County, Nevada, 1951-2008

USGS Publications Warehouse

Elliott, Peggy E.; Moreo, Michael T.

2011-01-01

From 1951 to 2008, groundwater withdrawals totaled more than 25,000 million gallons from wells on and directly adjacent to the Nevada National Security Site. Total annual groundwater withdrawals ranged from about 30 million gallons in 1951 to as much as 1,100 million gallons in 1989. Annual withdrawals from individual wells ranged from 0 million gallons to more than 325 million gallons. Monthly withdrawal data for the wells were compiled in a Microsoft(copyright) Excel 2003 spreadsheet. Groundwater withdrawal data are a compilation of measured and estimated withdrawals obtained from published and unpublished reports, U.S. Geological Survey files, and/or data reported by other agencies. The withdrawal data were collected from 42 wells completed in 33 boreholes. A history of each well is presented in terms of its well construction, borehole lithology, withdrawals, and water levels.

Blocking microglial pannexin-1 channels alleviates morphine withdrawal in rodents.

PubMed

Burma, Nicole E; Bonin, Robert P; Leduc-Pessah, Heather; Baimel, Corey; Cairncross, Zoe F; Mousseau, Michael; Shankara, Jhenkruthi Vijaya; Stemkowski, Patrick L; Baimoukhametova, Dinara; Bains, Jaideep S; Antle, Michael C; Zamponi, Gerald W; Cahill, Catherine M; Borgland, Stephanie L; De Koninck, Yves; Trang, Tuan

2017-03-01

Opiates are essential for treating pain, but termination of opiate therapy can cause a debilitating withdrawal syndrome in chronic users. To alleviate or avoid the aversive symptoms of withdrawal, many of these individuals continue to use opiates. Withdrawal is therefore a key determinant of opiate use in dependent individuals, yet its underlying mechanisms are poorly understood and effective therapies are lacking. Here, we identify the pannexin-1 (Panx1) channel as a therapeutic target in opiate withdrawal. We show that withdrawal from morphine induces long-term synaptic facilitation in lamina I and II neurons within the rodent spinal dorsal horn, a principal site of action for opiate analgesia. Genetic ablation of Panx1 in microglia abolished the spinal synaptic facilitation and ameliorated the sequelae of morphine withdrawal. Panx1 is unique in its permeability to molecules up to 1 kDa in size and its release of ATP. We show that Panx1 activation drives ATP release from microglia during morphine withdrawal and that degrading endogenous spinal ATP by administering apyrase produces a reduction in withdrawal behaviors. Conversely, we found that pharmacological inhibition of ATP breakdown exacerbates withdrawal. Treatment with a Panx1-blocking peptide ( 10 panx) or the clinically used broad-spectrum Panx1 blockers, mefloquine or probenecid, suppressed ATP release and reduced withdrawal severity. Our results demonstrate that Panx1-mediated ATP release from microglia is required for morphine withdrawal in rodents and that blocking Panx1 alleviates the severity of withdrawal without affecting opiate analgesia.

Reconstruction of global gridded monthly sectoral water withdrawals for 1971–2010 and analysis of their spatiotemporal patterns

DOE PAGES

Huang, Zhongwei; Hejazi, Mohamad; Li, Xinya; ...

2018-04-06

Human water withdrawal has increasingly altered the global water cycle in past decades, yet our understanding of its driving forces and patterns is limited. Reported historical estimates of sectoral water withdrawals are often sparse and incomplete, mainly restricted to water withdrawal estimates available at annual and country scales, due to a lack of observations at seasonal and local scales. In this study, through collecting and consolidating various sources of reported data and developing spatial and temporal statistical downscaling algorithms, we reconstruct a global monthly gridded (0.5°) sectoral water withdrawal dataset for the period 1971–2010, which distinguishes six water use sectors, i.e., irrigation,more » domestic, electricity generation (cooling of thermal power plants), livestock, mining, and manufacturing. Based on the reconstructed dataset, the spatial and temporal patterns of historical water withdrawal are analyzed. Results show that total global water withdrawal has increased significantly during 1971–2010, mainly driven by the increase in irrigation water withdrawal. Regions with high water withdrawal are those densely populated or with large irrigated cropland production, e.g., the United States (US), eastern China, India, and Europe. Seasonally, irrigation water withdrawal in summer for the major crops contributes a large percentage of total annual irrigation water withdrawal in mid- and high-latitude regions, and the dominant season of irrigation water withdrawal is also different across regions. Domestic water withdrawal is mostly characterized by a summer peak, while water withdrawal for electricity generation has a winter peak in high-latitude regions and a summer peak in low-latitude regions. Despite the overall increasing trend, irrigation in the western US and domestic water withdrawal in western Europe exhibit a decreasing trend. Our results highlight the distinct spatial pattern of human water use by sectors at the seasonal and annual timescales. Here, the reconstructed gridded water withdrawal dataset is open access, and can be used for examining issues related to water withdrawals at fine spatial, temporal, and sectoral scales.« less

Reconstruction of global gridded monthly sectoral water withdrawals for 1971–2010 and analysis of their spatiotemporal patterns

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

Huang, Zhongwei; Hejazi, Mohamad; Li, Xinya

Human water withdrawal has increasingly altered the global water cycle in past decades, yet our understanding of its driving forces and patterns is limited. Reported historical estimates of sectoral water withdrawals are often sparse and incomplete, mainly restricted to water withdrawal estimates available at annual and country scales, due to a lack of observations at seasonal and local scales. In this study, through collecting and consolidating various sources of reported data and developing spatial and temporal statistical downscaling algorithms, we reconstruct a global monthly gridded (0.5°) sectoral water withdrawal dataset for the period 1971–2010, which distinguishes six water use sectors, i.e., irrigation,more » domestic, electricity generation (cooling of thermal power plants), livestock, mining, and manufacturing. Based on the reconstructed dataset, the spatial and temporal patterns of historical water withdrawal are analyzed. Results show that total global water withdrawal has increased significantly during 1971–2010, mainly driven by the increase in irrigation water withdrawal. Regions with high water withdrawal are those densely populated or with large irrigated cropland production, e.g., the United States (US), eastern China, India, and Europe. Seasonally, irrigation water withdrawal in summer for the major crops contributes a large percentage of total annual irrigation water withdrawal in mid- and high-latitude regions, and the dominant season of irrigation water withdrawal is also different across regions. Domestic water withdrawal is mostly characterized by a summer peak, while water withdrawal for electricity generation has a winter peak in high-latitude regions and a summer peak in low-latitude regions. Despite the overall increasing trend, irrigation in the western US and domestic water withdrawal in western Europe exhibit a decreasing trend. Our results highlight the distinct spatial pattern of human water use by sectors at the seasonal and annual timescales. Here, the reconstructed gridded water withdrawal dataset is open access, and can be used for examining issues related to water withdrawals at fine spatial, temporal, and sectoral scales.« less

Reconstruction of global gridded monthly sectoral water withdrawals for 1971–2010 and analysis of their spatiotemporal patterns

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

Huang, Zhongwei; Hejazi, Mohamad; Li, Xinya

Human water withdrawal has increasingly altered the global water cycle in past decades, yet our understanding of its driving forces and patterns is limited. Reported historical estimates of sectoral water withdrawals are often sparse and incomplete, mainly restricted to water withdrawal estimates available at annual and country scales, due to a lack of observations at seasonal and local scales. In this study, through collecting and consolidating various sources of reported data and developing spatial and temporal statistical downscaling algorithms, we reconstruct a global monthly gridded (0.5°) sectoral water withdrawal dataset for the period 1971–2010, which distinguishes six water use sectors, i.e., irrigation,more » domestic, electricity generation (cooling of thermal power plants), livestock, mining, and manufacturing. Based on the reconstructed dataset, the spatial and temporal patterns of historical water withdrawal are analyzed. Results show that total global water withdrawal has increased significantly during 1971–2010, mainly driven by the increase in irrigation water withdrawal. Regions with high water withdrawal are those densely populated or with large irrigated cropland production, e.g., the United States (US), eastern China, India, and Europe. Seasonally, irrigation water withdrawal in summer for the major crops contributes a large percentage of total annual irrigation water withdrawal in mid- and high-latitude regions, and the dominant season of irrigation water withdrawal is also different across regions. Domestic water withdrawal is mostly characterized by a summer peak, while water withdrawal for electricity generation has a winter peak in high-latitude regions and a summer peak in low-latitude regions. Despite the overall increasing trend, irrigation in the western US and domestic water withdrawal in western Europe exhibit a decreasing trend. Our results highlight the distinct spatial pattern of human water use by sectors at the seasonal and annual timescales. The reconstructed gridded water withdrawal dataset is open access, and can be used for examining issues related to water withdrawals at fine spatial, temporal, and sectoral scales.« less

The spectroscopic impact of interactions with the four Gouterman orbitals from peripheral decoration of porphyrins with simple electron withdrawing and donating groups.

PubMed

Zhang, Angel; Kwan, Lydia; Stillman, Martin J

2017-11-07

Tetrapyrroles are of great interest for solar cell and photodynamic therapy applications due to their structural analogy with chlorophyll, a natural photosensitizer. Unsubstituted symmetric porphyrins exhibit weak absorption in the red region which makes them unsuitable for these applications. The push-pull peripheral decoration modifies the energies of the frontier molecular orbitals, which in turn influences the tetrapyrrole's spectroscopic properties. The absorption, magnetic circular dichroism, and emission spectra were measured for four zinc tetratolylporphyrin compounds substituted peripherally with a fused dimethoxybenzo group as an electron withdrawing group (EWG) on one pyrrole and on the opposite pyrrole, a single acetamido (1), a nitro (2), a proton (3), or a benzoylamino (4) substituent. Unusually, the magnetic circular dichroism spectrum of 2 exhibited a negative A term for the lowest energy absorption band (the Q band) and its emission spectrum was also unlike those of 1, 3, and 4. A complete computational analysis was carried out to obtain the energies and electron distribution, shown by electron density surfaces, of the four Gouterman MOs. TD-DFT calculations showed that for 2, ΔLUMO was greater than ΔHOMO, which accounted for the observed negative A term. The trend in the estimated MCD A term magnitudes, normalized to the absorbance as [A/(dipole strength) BM], provides experimental confirmation of the computationally determined ratio of ΔLUMO/ΔHOMO data. The value of ΔHOMO was confirmed by the trend in oscillator strengths. A series of fictive porphyrins (F1-F5) incorporating simple push-pull substituents were designed and their electronic structures were investigated using TD-DFT calculations. The substituents in the five fictive molecules illustrate the differential effect of the donor and acceptor groups in the β-position of the pyrroles on the relative stabilities of the four Gouterman orbitals. NO 2 groups result in the greatest splitting of the LUMO pair. We show that on using strong EWGs, opposite electron donating groups result in a ΔLUMO > 0, which red-shifts the Q band and introduces a strong dipole. With the nitro and formyl EWGs, ΔLUMO becomes greater than ΔHOMO, resulting in a complex electronic structure of the Q band, recognizable by a negative A term suggesting a design objective for future photosensitizers.

Opiate and opioid withdrawal

MedlinePlus

... opiate withdrawal; Oxycontin - opiate withdrawal; Hydrocodone - opiate withdrawal; Detox - opiates; Detoxification - opiates ... facilities set up to help people with detoxification (detox). In a regular hospital, if symptoms are severe. ...

Observed behaviours of pre-term children in a social play situation with classroom peers.

PubMed

Nadeau, Line; Tessier, Réjean; Descôteaux, Amélie

2009-08-01

A number of studies have reported social adjustment problems in pre-term children. To observe the pre-term's behaviour in an experimental situation and correlate these observed behaviours with the children's peer-rated social behaviours (withdrawal, aggression and sociability/leadership). Of 56 pre-term children, 24 were classified as the sick pre-term (SPT) group and 32 children as the healthy pre-term (HPT) group. The comparison group comprised 56 healthy full-terms. The experimental situation used a game called Rush Hour, a labyrinth-type board game. The play situation was videotaped and behaviours (number of consecutive moves) were coded in real time. At 12 years of age, the sick pre-term (SPT) group exhibited fewer consecutive moves during the game than the other two groups, especially when the task became more complex (involving four consecutives moves). Moreover, the Complex Task Index was correlated with the social withdrawal score rated by peers. The at-birth sick pre-term gradually became less involved in a complex decision-making task and this was understood as a lesser ability to make a decision in a complex setting.

Performance costs when emotion tunes inappropriate cognitive abilities: implications for mental resources and behavior.

PubMed

Storbeck, Justin

2012-08-01

Emotion tunes cognition, such that approach-motivated positive states promote verbal cognition, whereas withdrawal-motivated negative states promote spatial cognition (Gray, 2001). The current research examined whether self-control resources become depleted and influence subsequent behavior when emotion tunes an inappropriate cognitive tendency. In 2 experiments, either an approach-motivated positive state or a withdrawal-motivated negative state was induced, and then participants completed a verbal or a spatial working memory task creating conditions of emotion-cognition alignment (e.g., approach/verbal) or misalignment (e.g., approach/spatial). A control condition was also included. To examine behavioral costs due to depleted self-control resources, participants completed either a Stroop task (Stroop, 1935; Experiment 1) or a Black/White implicit association test (IAT; Greenwald, McGhee, & Schwartz, 1998; Experiment 2). Participants in the misalignment conditions performed worse on the Stroop task, and they were worse at controlling their implicit attitude biases on the IAT. Thus, when emotion tunes inappropriate cognitive tendencies for one's current environment, self-control resources become depleted, impairing behavioral control. (PsycINFO Database Record (c) 2012 APA, all rights reserved).

Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization.

PubMed

Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof

2008-09-24

High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required in order to avoid chain-breaking side reactions.

Cocaine withdrawal

MedlinePlus

... Substance use - cocaine withdrawal; Substance abuse - cocaine withdrawal; Drug abuse - cocaine withdrawal; Detox - cocaine ... Elsevier Saunders; 2016:chap 50. National Institute on Drug Abuse. What is cocaine? Updated May 2016. www.drugabuse. ...

Kinetic and Mechanistic Examination of Acid–Base Bifunctional Aminosilica Catalysts in Aldol and Nitroaldol Condensations

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

Collier, Virginia E.; Ellebracht, Nathan C.; Lindy, George I.

The kinetic and mechanistic understanding of cooperatively catalyzed aldol and nitroaldol condensations is probed using a series of mesoporous silicas functionalized with aminosilanes to provide bifunctional acid–base character. Mechanistically, a Hammett analysis is performed to determine the effects of electron-donating and electron-withdrawing groups of para-substituted benzaldehyde derivatives on the catalytic activity of each condensation reaction. This information is also used to discuss the validity of previously proposed catalytic mechanisms and to propose a revised mechanism with plausible reaction intermediates. For both reactions, electron-withdrawing groups increase the observed rates of reaction, though resonance effects play an important, yet subtle, role inmore » the nitroaldol condensation, in which a p-methoxy electron-donating group is also able to stabilize the proposed carbocation intermediate. Additionally, activation energies and pre-exponential factors are calculated via the Arrhenius analysis of two catalysts with similar amine loadings: one catalyst had silanols available for cooperative interactions (acid–base catalysis), while the other was treated with a silanol-capping reagent to prevent such cooperativity (base-only catalysis). The values obtained for activation energies and pre-exponential factors in each reaction are discussed in the context of the proposed mechanisms and the importance of cooperative interactions in each reaction. The catalytic activity decreases for all reactions when the silanols are capped with trimethylsilyl groups, and higher temperatures are required to make accurate rate measurements, emphasizing the vital role the weakly acidic silanols play in the catalytic cycles. The results indicate that loss of acid sites is more detrimental to the catalytic activity of the aldol condensation than the nitroaldol condensation, as evidenced by the significant decrease in the pre-exponential factor for the aldol condensation when silanols are unavailable for cooperative interactions. Cooperative catalysis is evidenced by significant changes in the pre-exponential factor, rather than the activation energy for the aldol condensation.« less

Kinetic and Mechanistic Examination of Acid–Base Bifunctional Aminosilica Catalysts in Aldol and Nitroaldol Condensations

DOE PAGES

Collier, Virginia E.; Ellebracht, Nathan C.; Lindy, George I.; ...

2015-12-09

The kinetic and mechanistic understanding of cooperatively catalyzed aldol and nitroaldol condensations is probed using a series of mesoporous silicas functionalized with aminosilanes to provide bifunctional acid–base character. Mechanistically, a Hammett analysis is performed to determine the effects of electron-donating and electron-withdrawing groups of para-substituted benzaldehyde derivatives on the catalytic activity of each condensation reaction. This information is also used to discuss the validity of previously proposed catalytic mechanisms and to propose a revised mechanism with plausible reaction intermediates. For both reactions, electron-withdrawing groups increase the observed rates of reaction, though resonance effects play an important, yet subtle, role inmore » the nitroaldol condensation, in which a p-methoxy electron-donating group is also able to stabilize the proposed carbocation intermediate. Additionally, activation energies and pre-exponential factors are calculated via the Arrhenius analysis of two catalysts with similar amine loadings: one catalyst had silanols available for cooperative interactions (acid–base catalysis), while the other was treated with a silanol-capping reagent to prevent such cooperativity (base-only catalysis). The values obtained for activation energies and pre-exponential factors in each reaction are discussed in the context of the proposed mechanisms and the importance of cooperative interactions in each reaction. The catalytic activity decreases for all reactions when the silanols are capped with trimethylsilyl groups, and higher temperatures are required to make accurate rate measurements, emphasizing the vital role the weakly acidic silanols play in the catalytic cycles. The results indicate that loss of acid sites is more detrimental to the catalytic activity of the aldol condensation than the nitroaldol condensation, as evidenced by the significant decrease in the pre-exponential factor for the aldol condensation when silanols are unavailable for cooperative interactions. Cooperative catalysis is evidenced by significant changes in the pre-exponential factor, rather than the activation energy for the aldol condensation.« less

THE PREVALENCE OF CANNABIS WITHDRAWAL AND ITS INFLUENCE ON ADOLESCENTS’ TREATMENT RESPONSE AND OUTCOMES: A 12-MONTH PROSPECTIVE INVESTIGATION

PubMed Central

Greene, M. Claire; Kelly, John F.

2014-01-01

Background Withdrawal, a diagnostic indicator of cannabis use disorder, is often minimized or ignored as a consequence of cannabis use, particularly among adolescents. This study aims to characterize cannabis withdrawal among adolescents in outpatient treatment for substance use disorder and evaluate the clinical significance of withdrawal as a predictor of substance-related outcomes. Methods Adolescent outpatients (N=127) reporting cannabis as their drug of choice (n=90) were stratified by presence of withdrawal and compared on demographic and clinical variables at treatment intake. Hierarchical linear models compared the effect of withdrawal on percent days abstinent (PDA) and related outcomes over a 1-year follow-up period. Results Adolescents reporting withdrawal (40%) were more likely to meet criteria for cannabis dependence, have higher levels of substance use severity, report more substance-related consequences, and have a mood disorder. Withdrawal was not associated with PDA over the follow-up period; however, this relationship was moderated by problem recognition such that adolescents reporting withdrawal and a drug problem improved at a greater rate with respect to PDA than those that didn’t recognize a problem with drugs and didn’t report withdrawal. Discussion Withdrawal is common among adolescent outpatients and is associated with a more clinically severe profile. In this sample, all adolescents reporting withdrawal met criteria for cannabis dependence, suggesting that withdrawal is a highly specific indicator of cannabis use disorder. While withdrawal doesn’t appear to be independently associated with substance use outcomes post-treatment, moderating factors such as drug problem recognition should be taken into account when formulating treatment and continuing care plans. PMID:25100311

Youth social withdrawal behavior (hikikomori): A systematic review of qualitative and quantitative studies.

PubMed

Li, Tim M H; Wong, Paul W C

2015-07-01

Acute and/or severe social withdrawal behavior among youth was seen as a culture-bound psychiatric syndrome in Japan, but more youth social withdrawal cases in different countries have been discovered recently. However, due to the lack of a formal definition and diagnostic tool for youth social withdrawal, cross-cultural observational and intervention studies are limited. We aimed to consolidate existing knowledge in order to understand youth social withdrawal from diverse perspectives and suggest different interventions for different trajectories of youth social withdrawal. This review examined the current available scientific information on youth social withdrawal in the academic databases: ProQuest, ScienceDirect, Web of Science and PubMed. We included quantitative and qualitative studies of socially withdrawn youths published in English and academic peer-reviewed journals. We synthesized the information into the following categories: (1) definitions of youth social withdrawal, (2) developmental theories, (3) factors associated with youth social withdrawal and (4) interventions for socially withdrawn youths. Accordingly, there are diverse and controversial definitions for youth social withdrawal. Studies of youth social withdrawal are based on models that lead to quite different conclusions. Researchers with an attachment perspective view youth social withdrawal as a negative phenomenon, whereas those who adopt Erikson's developmental theory view it more positively as a process of seeking self-knowledge. Different interventions for socially withdrawn youths have been developed, mainly in Japan, but evidence-based practice is almost non-existent. We propose a theoretical framework that views youth social withdrawal as resulting from the interplay between psychological, social and behavioral factors. Future validation of the framework will help drive forward advances in theory and interventions for youth social withdrawal as an emerging issue in developed countries. © The Royal Australian and New Zealand College of Psychiatrists 2015.

Withdrawal Method (Coitus Interruptus)

MedlinePlus

Withdrawal method (coitus interruptus) Overview The withdrawal method of contraception, also known as coitus interruptus, is the practice of withdrawing the penis from the vagina and away from a woman's external ...

29 CFR 1956.24 - Procedures for withdrawal of approval.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 9 2010-07-01 2010-07-01 false Procedures for withdrawal of approval. 1956.24 Section 1956..., Change, Evaluation and Withdrawal of Approval Procedures § 1956.24 Procedures for withdrawal of approval... withdrawal of approval of plans approved under this part 1956, except that (because these plans, as do public...

40 CFR 97.86 - Withdrawal from NOX Budget Trading Program.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Withdrawal from NOX Budget Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Individual Unit Opt-ins § 97.86 Withdrawal from NOX Budget Trading Program. (a) Requesting withdrawal. To withdraw...

40 CFR 97.86 - Withdrawal from NOX Budget Trading Program.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Withdrawal from NOX Budget Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Individual Unit Opt-ins § 97.86 Withdrawal from NOX Budget Trading Program. (a) Requesting withdrawal. To withdraw...

40 CFR 97.86 - Withdrawal from NOX Budget Trading Program.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Withdrawal from NOX Budget Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Individual Unit Opt-ins § 97.86 Withdrawal from NOX Budget Trading Program. (a) Requesting withdrawal. To withdraw...

Chemical structure-based predictive model for the oxidation of trace organic contaminants by sulfate radical.

PubMed

Ye, Tiantian; Wei, Zongsu; Spinney, Richard; Tang, Chong-Jian; Luo, Shuang; Xiao, Ruiyang; Dionysiou, Dionysios D

2017-06-01

Second-order rate constants [Formula: see text] for the reaction of sulfate radical anion (SO 4 •- ) with trace organic contaminants (TrOCs) are of scientific and practical importance for assessing their environmental fate and removal efficiency in water treatment systems. Here, we developed a chemical structure-based model for predicting [Formula: see text] using 32 molecular fragment descriptors, as this type of model provides a quick estimate at low computational cost. The model was constructed using the multiple linear regression (MLR) and artificial neural network (ANN) methods. The MLR method yielded adequate fit for the training set (R training 2 =0.88,n=75) and reasonable predictability for the validation set (R validation 2 =0.62,n=38). In contrast, the ANN method produced a more statistical robustness but rather poor predictability (R training 2 =0.99andR validation 2 =0.42). The reaction mechanisms of SO 4 •- reactivity with TrOCs were elucidated. Our result shows that the coefficients of functional groups reflect their electron donating/withdrawing characters. For example, electron donating groups typically exhibit positive coefficients, indicating enhanced SO 4 •- reactivity. Electron withdrawing groups exhibit negative values, indicating reduced reactivity. With its quick and accurate features, we applied this structure-based model to 55 discrete TrOCs culled from the Contaminant Candidate List 4, and quantitatively compared their removal efficiency with SO 4 •- and OH in the presence of environmental matrices. This high-throughput model helps prioritize TrOCs that are persistent to SO 4 •- based oxidation technologies at the screening level, and provide diagnostics of SO 4 •- reaction mechanisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ynamides in Ring Forming Transformations

PubMed Central

WANG, XIAO-NA; YEOM, HYUN-SUK; FANG, LI-CHAO; HE, SHUZHONG; MA, ZHI-XIONG; KEDROWSKI, BRANT L.; HSUNG, RICHARD P.

2013-01-01

Conspectus The ynamide functional group activates carbon-carbon triple bonds through an attached nitrogen atom that bears an electron-withdrawing group. As a result, the alkyne has both electrophilic and nucleophilic properties. Through the selection of the electron-withdrawing group attached to nitrogen chemists can modulate the electronic properties and reactivity of ynamides, making these groups versatile synthetic building blocks. The reactions of ynamides also lead directly to nitrogen-containing products, which provides access to important structural motifs found in natural products and molecules of medicinal interest. Therefore, researchers have invested increasing time and research in the chemistry of ynamides in recent years. This Account surveys and assesses new organic transformations involving ynamides developed in our laboratory and in others around the world. We showcase the synthetic power of ynamides for rapid assembly of complex molecular structures. Among the recent reports of ynamide transformations, ring-forming reactions provide a powerful tool for generating molecular complexity quickly. In addition to their synthetic utility, such reactions are mechanistically interesting. Therefore, we focus primarily on the cyclization chemistry of ynamides. This Account highlights ynamide reactions that are useful in the rapid synthesis of cyclic and polycyclic structural manifolds. We discuss the mechanisms active in the ring formations and describe representative examples that demonstrate the scope of these reactions and provide mechanistic insights. In this discussion we feature examples of ynamide reactions involving radical cyclizations, ring-closing metathesis, transition metal and non-transition metal mediated cyclizations, cycloaddition reactions, and rearrangements. The transformations presented rapidly introduce structural complexity and include nitrogen within, or in close proximity to, a newly formed ring (or rings). Thus, ynamides have emerged as powerful synthons for nitrogen-containing heterocycles and nitrogen-substituted rings, and we hope this Account will promote continued interest in the chemistry of ynamides. PMID:24164363

First- versus second-generation electronic cigarettes: predictors of choice and effects on urge to smoke and withdrawal symptoms.

PubMed

Dawkins, Lynne; Kimber, Catherine; Puwanesarasa, Yasothani; Soar, Kirstie

2015-04-01

To (1) estimate predictors of first- versus second-generation electronic cigarette (e-cigarette) choice; and (2) determine whether a second-generation device was (i) superior for reducing urge to smoke and withdrawal symptoms (WS) and (ii) associated with enhanced positive subjective effects. Mixed-effects experimental design. Phase 1: reason for e-cigarette choice was assessed via questionnaire. Phase 2: participants were allocated randomly to first- or second-generation e-cigarette condition. Urge to smoke and WS were measured before and 10 minutes after taking 10 e-cigarette puffs. University of East London, UK. A total of 97 smokers (mean age 26; standard deviation 8.7; 54% female). Single-item urge to smoke scale to assess craving and the Mood and Physical Symptoms Scale (MPSS) to assess WS. Subjective effects included: satisfaction, hit, 'felt like smoking' and 'would use to stop smoking' (yes versus no response). Equal numbers chose each device, but none of the predictor variables (gender, age, tobacco dependence, previous e-cigarette use) accounted for choice. Only baseline urge to smoke/WS predicted urge to smoke/WS 10 minutes after use (B =0.38; P <0.001 and B =0.53; P <0.001). E-cigarette device was not a significant predictor. Those using the second-generation device were more likely to report satisfaction and use in a quit attempt (χ(2)  = 12.10, P =0.001 and χ(2)  = 5.53, P =0.02). First- and second-generation electronic cigarettes appear to be similarly effective in reducing urges to smoke during abstinence, but second-generation devices appear to be more satisfying to users. © 2014 Society for the Study of Addiction.

Clinical significance of early smoking withdrawal effects and their relationships with nicotine metabolism: preliminary results from a pilot study.

PubMed

Hendricks, Peter S; Delucchi, Kevin L; Benowitz, Neal L; Hall, Sharon M

2014-05-01

Although the early time course of smoking withdrawal effects has been characterized, the clinical significance of early withdrawal symptoms and their predictors are unknown. This study evaluated the relationships of early smoking withdrawal effects with quit attempt outcomes and the rate of nicotine metabolism. Eleven treatment-seeking smokers abstained from smoking for 4 hr in the laboratory before a quit attempt. Withdrawal measures included heart rate, sustained attention, and self-report. Following baseline assessment, withdrawal measures were administered every 30 min. At the conclusion of the 4-hr early withdrawal session, participants received a brief smoking cessation intervention and then returned 1 week and 12 weeks later for outcome assessments that included biochemically confirmed smoking abstinence, cigarettes smoked in the past 24hr, and self-reported withdrawal symptoms. The rate of nicotine metabolism was estimated at intake with the nicotine metabolite ratio (trans-3'-hydroxycotinine/cotinine) measured in saliva. Greater self-reported negative affect and concentration difficulty during early withdrawal, most notably anxiety, were related with poorer quit attempt outcomes. There was some indication that although a faster increase in craving and greater hunger during early withdrawal were associated with more favorable outcomes, a greater decrease in heart rate during this time was associated with poorer outcomes. Faster nicotine metabolism was related to a faster increase in anxiety but a slower increase in craving during early withdrawal. These findings lend support to the clinical significance of early smoking withdrawal effects. The rate of nicotine metabolism may be a useful predictor of early withdrawal symptoms.

Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.

PubMed

Singh, Nakul; O'Malley, Patrick J; Popelier, Paul L A

2005-02-21

Density functional calculations using the B3LYP functional are used to provide insight into the hydrogen abstraction mechanism of phenolic antioxidants. The energy profiles for 13 ortho, meta, para and di-methyl substituted phenols with hydroperoxyl radical have been determined. An excellent correlation between the enthalpy (DeltaH) and activation energy (DeltaEa) was found, obeying the Evans-Polanyi rule. The effects of hydrogen bonding on DeltaEa are also discussed. Electron donating groups at the ortho and para positions are able to lower the activation energy for hydrogen abstraction. The highly electron withdrawing fluoro substituent increases the activation energies relative to phenol at the meta position but not at the para position. The electron density is studied using the atoms in molecules (AIM) approach. Atomic and bond properties are extracted to describe the hydrogen atom abstraction mechanism. It is found that on going from reactants to transition state, the hydrogen atom experiences a loss in volume, electronic population and dipole moment. These features suggest that the phenol hydroperoxyl reactions proceed according to a proton coupled electron transfer (PCET) as opposed to a hydrogen atom transfer (HAT) mechanism.

Estimated water use in Arkansas, 2010

USGS Publications Warehouse

Pugh, Aaron L.; Holland, Terrance W.

2015-01-01

Groundwater withdrawals comprised about 69 percent of the total amount of water used in Arkansas in 2010. Four aquifers in Arkansas account for more than 99 percent of the total groundwater withdrawals. The aquifers in deposits of Quaternary age supplied about 97 percent of all groundwater withdrawals. The Sparta-Memphis aquifer supplied about 2.5 percent of all groundwater withdrawals, the Wilcox aquifer supplied about 0.5 percent of all groundwater withdrawals, and the Paleozoic aquifer supplied about 0.3 percent of all groundwater withdrawals.

Infants in Drug Withdrawal: A National Description of Nurse Workload, Infant Acuity, and Parental Needs.

PubMed

Smith, Jessica G; Rogowski, Jeannette A; Schoenauer, Kathryn M; Lake, Eileen T

Infants in drug withdrawal have complex physiological and behavioral states, requiring intensive nursing care. The study objectives were to describe acuity, parental needs, and nurse workload of infants in drug withdrawal compared with other infants. The design was cross-sectional and involved secondary nurse survey data from 6045 staff nurses from a national sample of 104 neonatal intensive care units. Nurses reported the care of 15 233 infants, 361 (2.4%) of whom were in drug withdrawal. Three-fourths of hospitals had at least 1 infant in drug withdrawal. In these hospitals, the mean number of infants in drug withdrawal was 4.7. Infant acuity was significantly higher among infants in drug withdrawal. Parents of infants in drug withdrawal required significantly more care to address complex social situations (51% vs 12%). The number of infants assigned to nurses with at least 1 infant in withdrawal (mean = 2.69) was significantly higher than typical (mean = 2.51). Given infant acuity and parental needs, policies legislating patient-to-nurse ratios should permit professional discretion on the number of patients to assign nurses caring for infants in drug withdrawal. Managers and charge nurses should consider the demands of caring for infants in drug withdrawal in assignment decisions and provide support and education.

Importance of phenols structure on their activity as antinitrosating agents: A kinetic study

PubMed Central

Pessêgo, Márcia; Rosa da Costa, Ana M; Moreira, José A.

2011-01-01

Objective: Nitrosative deamination of DNA bases induced by reaction with reactive nitrogen species (RNS) has been pointed out as a probable cause of mutagenesis. (Poly)phenols, present in many food items from the Mediterranean diet, are believed to possess antinitrosating properties due to their RNS scavenging ability, which seems to be related to their structure. It has been suggested that phenolic compounds will react with the above-mentioned species more rapidly than most amino compounds, thus preventing direct nitrosation of the DNA bases and their transnitrosation from endogenous N-nitroso compounds, or most likely from the transient N-nitrosocompounds formed in vivo. Materials and Methods: In order to prove that assumption, a kinetic study of the nitroso group transfer from a N-methyl-N-nitrosobenzenesulfonamide (N-methyl-N-nitroso-4-methylbenzenesulfonamide, MeNMBS) to the DNA bases bearing an amine group and to a series of phenols was carried out. In the transnitrosation of phenols, the formation of nitrosophenol was monitored by Ultraviolet (UV) / Visible spectroscopy, and in the reactions of the DNA bases, the consumption of MeNMBS was followed by high performance liquid chromatography (HPLC). Results: The results obtained point to the transnitrosation of DNA bases being negligible, as well as that of phenols bearing electron-withdrawing groups. Phenols with methoxy substituents in positions 2, 4, and / or 6, although they seemed to react, did not afford the expected product. Phenols with electron-releasing substituents, unless these blocked the oxygen atom, reacted with our model compound at an appreciable rate. O-nitrosation of the phenolate ion followed by rearrangement of the C-nitrosophenol seemed to be involved. Conclusion: This study provided evidence that the above compounds might actually act as antinitrosating agents in vivo. PMID:21430963

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.

Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kim, Dong Young; Park, Hosang; Choi, Woon Ih; Roy, Basab; Seo, Jinah; Park, Insun; Kim, Jin Hae; Park, Jong Hwan; Kang, Yoon-Sok; Koh, Meiten

2017-07-01

Tris(trimethylsilyl) phosphite (P(OSi(CH3)3)3) is a multifunctional electrolyte additive for scavenging HF and forming a cathode electrolyte interphase (CEI). Systematic analysis of the HF reaction pathways and redox potentials of P(OSi(CH3)3)3, OP(OSi(CH3)3)3, P(OSiF3)3, and OP(OSiF3)3, and their reaction products, using ab initio calculations allowed us to elucidate the operating mechanism of P(OSi(CH3)3)3 and verify the rules that determine its HF reaction pathways and electrochemical stability. While Osbnd Si cleavage is the predominant HF scavenging pathway for P(OSi(CH3)3)3, Osbnd P cleavage is stabilized by replacing CH3 with an electron-withdrawing group. Thus, P(OSiF3)3 scavenges HF mainly through Osbnd P cleavage to produce PF3, which has high oxidation stability. However, the Osbnd Si cleavage pathway produces P(OSi(CH3)3)2OH, P(OSi(CH3)3) (OH)2, and P(OH)3 sequentially, along with Si(CH3)3F. These PO3 systems, which are oxidized earlier than carbonate solutions and form tightly bonded units following oxidation, act as seed units for compact CEI growth. Moreover, the HF scavenging ability of PO3 systems is maintained during oxidation until all Osbnd Si bonds are broken. As a strategy for developing additives with enhanced functionality, modifying P(OSi(CH3)3)3 by replacing CH3 with an electron-donating group to exclusively utilize the Osbnd Si cleavage pathway for HF scavenging is recommended.

Simulation of groundwater flow and hydrologic effects of groundwater withdrawals from the Kirkwood-Cohansey aquifer system in the Pinelands of southern New Jersey

USGS Publications Warehouse

Charles, Emmanuel; Nicholson, Robert S.

2012-01-01

The Kirkwood-Cohansey aquifer system is an important source of present and future water supply in southern New Jersey. Because this unconfined aquifer system also supports sensitive wetland and aquatic habitats within the New Jersey Pinelands (Pinelands), water managers and policy makers need up-to-date information, data, and projections that show the effects of potential increases in groundwater withdrawals on these habitats. Finite-difference groundwater flow models (MODFLOW) were constructed for three drainage basins (McDonalds Branch Basin, 14.3 square kilometers (km2); Morses Mill Stream Basin, 21.63 km2; and Albertson Brook Basin, 52.27 km2) to estimate the effects of potential increases in groundwater withdrawals on water levels and the base-flow portion of streamflow, in wetland and aquatic habitats. Three models were constructed for each drainage basin: a transient model consisting of twenty-four 1-month stress periods (October 2004 through September 2006); a transient model to simulate the 5- to 10-day aquifer tests that were performed as part of the study; and a high-resolution, steady-state model used to assess long-term effects of increased groundwater withdrawals on water levels in wetlands and on base flow. All models were constructed with the same eight-layer structure. The smallest horizontal cell dimensions among the three model areas were 150 meters (m) for the 24-month transient models, 10 m for the steady-state models, and 3 m for the transient aquifer-test models. Boundary flows of particular interest to this study and represented separately are those for wetlands, streams, and evapotranspiration. The final variables calibrated from both transient models were then used in steady-state models to assess the long-term effects of increased groundwater withdrawals on water levels in wetlands and on base flow. Results of aquifer tests conducted in the three study areas illustrate the effects of withdrawals on water levels in wetlands and on base flow. Pumping stresses at aquifer-test sites resulted in measurable drawdown in each observation well installed for the tests. The magnitude of drawdown in shallow wetland observation wells at the end of pumping ranged from 5.5 to 16.7 centimeters (cm). The stresses induced by the respective tests reduced the flow of the smallest stream (McDonalds Branch) by 75 percent and slightly reduced flow in a side channel of Morses Mill Stream, but did not measurably affect the flow of Morses Mill Stream or Albertson Brook. Results of aquifer-test simulations were used to refine the estimates of hydraulic properties used in the models and to confirm the ability of the model to replicate observed hydrologic responses to pumping. Steady-state sensitivity simulation results for a variety of single well locations and depths were used to define overall “best-case” (smallest effect on wetland water levels and base flow) and “worst-case” (greatest effect on wetland water levels and base flow) groundwater withdrawal configurations. “Best-case” configurations are those for which the extent of the wetland areas within a 1-kilometer (km) radius of the withdrawal well is minimized, the well is located at least 100 m and as far from wetland boundaries as possible, and the withdrawal is from a deep well (50–90 m deep). “Worst-case” configurations are those for which the extent of wetlands within a 1-km radius of the withdrawal well is maximized, the well is located 100 m or less from a wetland boundary, and the withdrawal is from a relatively shallow well (30–67 m deep). “Best-” and “worst-case” simulations were applied by locating hypothetical wells across the study areas and assigning groundwater withdrawals so that the sum of the withdrawals for the basin is equal to 5, 10, 15, and 30 percent of overall recharge. The results were compared to the results of simulations of no groundwater withdrawals. Results for withdrawals of 5 percent of recharge show that the area of wetland water-level decline that exceeded 15 cm was as much as 1.5 percent of the total wetland area for the “best-case” simulations and as much as 9.7 percent of the total wetland area for the “worst-case” simulations. For the same withdrawals, base-flow reduction was as much as 5.1 percent for the “best-case” simulations and as much as 8.6 percent for the “worst-case” simulations. Results for withdrawals of 30 percent of recharge show that the area of wetland water-level decline that exceeded 15 cm was as much as 70 percent of the total wetland area for the “best-case” simulations and as much as 84 percent of the total wetland area for the “worst-case” simulations. For the same withdrawals, base-flow reduction was as much as 30 percent for the “best-case” simulations and as much as 51 percent for the “worst-case” simulations. Results for withdrawals of 10 and 15 percent of recharge show decreased water levels and base flow that are intermediate between those simulated for 5 and 30 percent of recharge. Several approaches for applying the results of this study to other parts of the Pinelands were explored. An analytical-modeling technique based on the Thiem equation and image-well theory was developed to estimate local drawdown distributions resulting from withdrawals in other areas within the Pinelands. Results of example applications of this technique were compared with those of the numerical simulations used in this study and were shown to be useful. Differences among the three basins in the simulated percentage of basin wetlands affected by drawdown were found to be related to the proximity of wetlands to streams, the proximity of wetlands to pumped wells, and the vertical conductance of the aquifer system. These factors formed the basis for an index of wetland vulnerability to drawdown. An empirically-derived model based on the Gompertz function and the wetland vulnerability index was developed, tested, and shown to be an effective means to evaluate potential drawdown in wetlands at a basin scale throughout the Pinelands. Base-flow reduction can be estimated from generalized results of the numerical models, estimates of evapotranspiration reduction, or available regional groundwater flow models. These approaches could be used to evaluate alternative water-supply strategies and, in conjunction with ecological-modeling results, to determine maximum basin withdrawal rates within the limits of acceptable ecological change.

5 CFR 1650.41 - How to obtain an age-based withdrawal.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 5 Administrative Personnel 3 2011-01-01 2011-01-01 false How to obtain an age-based withdrawal... an age-based withdrawal. To request an age-based withdrawal, a participant must submit to the TSP record keeper a properly completed paper TSP age-based withdrawal request form or use the TSP Web site to...

5 CFR 1650.41 - How to obtain an age-based withdrawal.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 5 Administrative Personnel 3 2013-01-01 2013-01-01 false How to obtain an age-based withdrawal... an age-based withdrawal. To request an age-based withdrawal, a participant must submit to the TSP record keeper a properly completed paper TSP age-based withdrawal request form or use the TSP Web site to...

5 CFR 1650.41 - How to obtain an age-based withdrawal.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 5 Administrative Personnel 3 2012-01-01 2012-01-01 false How to obtain an age-based withdrawal... an age-based withdrawal. To request an age-based withdrawal, a participant must submit to the TSP record keeper a properly completed paper TSP age-based withdrawal request form or use the TSP Web site to...

Substituent effects on furan-phenylene copolymer for photovoltaic improvement: A density functional study

NASA Astrophysics Data System (ADS)

Janprapa, Nuttaporn; Vchirawongkwin, Viwat; Kritayakornupong, Chinapong

2018-06-01

The structural, electronic and photovoltaic properties of furan-phenylene copolymer ((Fu-co-Ph)4) and its derivatives were evaluated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The calculated band gaps of pristine furan and phenylene are in good agreement with the available experimental data. The lower band gap value of 2.72 eV was obtained from -NO2 and -NHCH3 substituents, leading to broader solar absorption range. With respected to the reorganization energy, -OCH3, -NHCH3, -OH, -SCH3, -CH3, -CF3, -NO2, and -F substituted (Fu-co-Ph)4 structures were classified as better electron donor materials. For combination with PC61BM, -NO2, -CN, -CF3 and -F functionalized copolymers demonstrated significantly higher open circuit voltage (Voc) values ranging from 1.07 to 2.10 eV. Our results revealed that electron withdrawing group substitution on furan-phenylene copolymers was an effective way for improving electronic and optical properties of donor materials used in photovoltaic applications.

A precipitation-runoff model for analysis of the effects of water withdrawals on streamflow, Ipswich River basin, Massachusetts

USGS Publications Warehouse

Zarriello, Phillip J.; Ries, Kernell G.

2000-01-01

Water withdrawals from the 155-square-mile Ipswich River Basin in northeastern Massachusetts affect aquatic habitat, water quality, and recreational use of the river. To better understand the effects of these withdrawals on streamflow, particularly low flow, the Hydrological Simulation Program-FORTRAN (HSPF) was used to develop a watershed-scale precipitation-runoff model of the Ipswich River to simulate its hydrology and complex water-use patterns.An analytical solution was used to compute time series of streamflow depletions resulting from ground-water withdrawals at wells. The flow depletions caused by pumping from the wells were summed along with any surface-water withdrawals to calculate the total withdrawal along a stream reach. The water withdrawals, records of precipitation, and streamflow records on the Ipswich River at South Middleton and at Ipswich for the period 1989?93 were used to calibrate the model. Model-fit analysis indicates that the simulated flows matched observed flows over a wide range of conditions; at a minimum, the coefficient of model-fit efficiency indicates that the model explained 79 percent of the variance in the observed daily flow.Six alternative water-withdrawal and land-use scenarios were simulated with the model. Three scenarios were examined for the 1989?93 calibration period, and three scenarios were examined for the 1961?95 period to test alternative withdrawals and land use over a wider range of climatic conditions, and to compute 1-, 7-, and 30-day low-flow frequencies using a log-Pearson Type III analysis. Flow-duration curves computed from results of the 1989?93 simulations indicate that, at the South Middleton and Ipswich gaging stations, streamflows when no water withdrawals are being made are nearly identical to streamflows when no ground-water withdrawals are made. Streamflow under no water withdrawals at both stations are about an order of magnitude larger at the 99.8 percent exceedence probability than simulations with only ground-water withdrawals. Long-term simulations indicate that the differences between streamflow with no water withdrawals and average 1989?93 water withdrawals is similar to the difference between simulations for the same water-use conditions made for the 1989?93 period at both sites. The 7-day, 10-year low-flow (7Q10, a widely used regulatory statistic) at the South Middleton station was 4.1 cubic feet per second (ft3/s) with no water withdrawals and 1991 land use, 5.8 ft3/s no withdrawals and undeveloped land, and 0.54 ft3/s with average 1989?93 water withdrawals and 1991 land use. The 7Q10 at the Ipswich station was about 8.3 ft3/s for simulations with no water withdrawals for both the 1991 land use and the undeveloped land conditions, and 2.7 ft3/s for simulations with average 1989?93 water withdrawals and 1991 land use. Simulation results indicate that surface-water withdrawals have little effect on the duration and frequency of low flows, but the cumulative ground-water withdrawals substantially decrease low flows.

Nicotine Withdrawal; Measure Your Symptoms (Quiz)

MedlinePlus

... Free Resources Medications Can Help You Quit Using Nicotine Replacement Therapy Busting NRT Myths Smokefree Phone Apps ... Withdrawal Understanding Withdrawal Quiz: How Strong is Your Nicotine Addiction? Quiz: What Are Your Withdrawal Symptoms? Dealing ...

The Cannabis Withdrawal Scale development: patterns and predictors of cannabis withdrawal and distress.

PubMed

Allsop, David J; Norberg, Melissa M; Copeland, Jan; Fu, Shanlin; Budney, Alan J

2011-12-01

Rates of treatment seeking for cannabis are increasing, and relapse is common. Management of cannabis withdrawal is an important intervention point. No psychometrically sound measure for cannabis withdrawal exists, and as a result treatment developments cannot be optimally targeted. The aim is to develop and test the psychometrics of the Cannabis Withdrawal Scale and use it to explore predictors of cannabis withdrawal. A volunteer sample of 49 dependent cannabis users provided daily scores on the Cannabis Withdrawal Scale during a baseline week and 2 weeks of abstinence. Internal reliability (Cronbach's alpha=0.91), test-retest stability (average intra-class correlation=0.95) and content validity analysis show that the Cannabis Withdrawal Scale has excellent psychometric properties. Nightmares and/or strange dreams was the most valid item (Wald χ²=105.6, P<0.0001), but caused relatively little associated distress (Wald χ²=25.11, P=0.03). Angry outbursts were considered intense (Wald χ²=73.69, P<0.0001) and caused much associated distress (Wald χ²=45.54, P<0.0001). Trouble getting to sleep was also an intense withdrawal symptom (Wald χ²=42.31, P<0.0001) and caused significant associated distress (Wald χ²=47.76, P<0.0001). Scores on the Severity of Dependence Scale predicted cannabis withdrawal. The Cannabis Withdrawal Scale can be used as a diagnostic instrument in clinical and research settings where regular monitoring of withdrawal symptoms is required. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Structural and morphological study of ZrO2 thin films

NASA Astrophysics Data System (ADS)

Kumar, Davinder; Singh, Avtar; Kaur, Manpreet; Rana, Vikrant Singh; Kaur, Raminder

2018-05-01

In this paper we discuss the fabrication of transparent thin films of Zirconium Oxide (ZrO2) deposited on glass substrates by sol-gel dip coating technique. Further these fabricated films were characterized for different annealing temperatures and withdrawal speed. X-ray diffraction is used to study the structural properties of deposited thin films and it reveals the change in crystallographic properties with the change in annealing temperature. Thickness of thin films is estimated by using scanning electron microscope.

Picolinoxy group, a new leaving group for anti SN2' selective allylic substitution with aryl anions based on Grignard reagents.

PubMed

Kiyotsuka, Yohei; Acharya, Hukum P; Katayama, Yuji; Hyodo, Tomonori; Kobayashi, Yuichi

2008-05-01

The picolinoxy group was found to be an extremely powerful leaving group for allylic substitution with aryl nucleophiles derived from ArMgBr and CuBr*Me2S. The substitution proceeds with anti SN2' pathway and with high chirality transfer. The electron-withdrawing effect of the pyridyl group and chelation to MgBr2 are likely the origin of success. Results suggesting these effects were obtained.

Synthesis and cytotoxicity of 2,5-dihydroxychalcones and related compounds.

PubMed

Nam, Nguyen-Hai; Hong, Dong-Ho; You, Young-Jae; Kim, Yong; Bang, Seong-Cheol; Kim, Hwan-Mook; Ahn, Byung-Zun

2004-06-01

A series of 2, 5-dihydroxychalcones and related compounds were synthesized, and their cytotoxicities against tumor cell lines and human umbilical venous endothelial cells (HUVEC) evaluated. It was found that chalcones, with electron-withdrawing substituents on an A ring, exhibited significant cytotoxicities. Among the synthesized compounds, 2'-chloro-2, 5-dihydroxychalcone (9) was most potent, with an IC50 value as low as 0.31 microg/mL. This compound also exhibited a significant cytotoxic selectivity toward HUVEC.

Protecting Group and Solvent Control of Stereo- and Chemoselectivity in Glucal 3-Carbamate Amidoglycosylation

PubMed Central

Gupta, Ritu; Sogi, Kimberly M.; Bernard, Sarah E.; Decatur, John D.; Rojas, Christian M.

2009-01-01

In the Rh2(OAc)4-catalyzed amidoglycosylation of glucal 3-carbamates, anomeric stereoselectivity and the extent of competing C3–H oxidation depend on the 4O and 6O protecting groups. Acyclic protection permits high α-anomer selectivity with further improvement in less polar solvents, while electron-withdrawing protecting groups limit C3-oxidized byproducts. Stereocontrol and bifurcation between alkene insertion and C3–H oxidation reflect an interplay of conformational, stereoelectronic, and inductive factors. PMID:19254041

2,3-Dihydroxybenzoic acid amides of tetraazaalkanes and tetaaza cycloalkanes

DOEpatents

Weitl, F.L.; Raymond, K.N.

1980-01-01

This disclosure is directed to a compound of the formula given in the patent wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO[sub 3]H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes. No Drawings

Breast Tumor pH: Design, Evaluation, and Application of Novel Reporter Molecules

DTIC Science & Technology

2001-10-01

DM, Burton DJ. J. Am Chem Soc. 1986, 108, 832. 8. Urata , H, Fuchikami T. Tet. Letters 1991,91. 9. Mehta, VD, Kulkarni PV, Mason RP, et al. 6...substitution reaction on an aryl iodide with trifluoromethyl copper ("CuCF3") [7]. Urata [8] described a convenient method for the in situ generation of...the stronger electron-withdrawing nature of the CF3 group causes this marked increase in acidity, which makes 6-CF3POL a better probe for

The parents' ability to take care of their baby as a factor in decisions to withhold or withdraw life-prolonging treatment in two Dutch NICUs.

PubMed

Moratti, Sofia

2010-06-01

In The Netherlands, it is openly acknowledged that the parents' ability to take care of their child plays a role in the decision-making process over administration of life-prolonging treatment to severely defective newborn babies. Unlike other aspects of such decision-making process up until the present time, the 'ability to take care' has not received specific attention in regulation or in empirical research. The present study is based on interviews with neonatologists in two Dutch NICUs concerning their definition of the ability to take care and its relevance in non-treatment decisions. All of the respondents think that the ability to take care consists of more than one factor. Most doctors mention the parents' emotional state, social network and cognitive abilities. Some doctors mention the presence of psychological conditions in the parents, their financial situation and physical condition. A few refer to the parents' experience and age, their chances to have another baby and their cultural background. Most doctors think the ability to take care has a secondary relevance in the decision-making process, while the primary concern is assessing the condition of the child. A substantial minority thinks the ability to take care does not play any role, while one doctor thinks it is a factor of primary importance. The study constitutes an important stepping-stone for future research in The Netherlands and elsewhere.

Two-photon or higher-order absorbing optical materials and methods of use

NASA Technical Reports Server (NTRS)

Marder, Seth (Inventor); Perry, Joseph (Inventor)

2012-01-01

Compositions capable of simultaneous two-photon absorption and higher order absorptivities are provided. Compounds having a donor-pi-donor or acceptor-pi-acceptor structure are of particular interest, where the donor is an electron donating group, acceptor is an electron accepting group, and pi is a pi bridge linking the donor and/or acceptor groups. The pi bridge may additionally be substituted with electron donating or withdrawing groups to alter the absorptive wavelength of the structure. Also disclosed are methods of generating an excited state of such compounds through optical stimulation with light using simultaneous absorption of photons of energies individually insufficient to achieve an excited state of the compound, but capable of doing so upon simultaneous absorption of two or more such photons. Applications employing such methods are also provided, including controlled polymerization achieved through focusing of the light source(s) used.

Heterocyclic Schiff bases as non toxic antioxidants: Solvent effect, structure activity relationship and mechanism of action

NASA Astrophysics Data System (ADS)

Shanty, Angamaly Antony; Mohanan, Puzhavoorparambil Velayudhan

2018-03-01

Phenolic heterocyclic imine based Schiff bases from Thiophene-2-carboxaldehyde and Pyrrole-2-carboxaldehyde were synthesized and characterized as novel antioxidants. The solvent effects of these Schiff bases were determined and compared with standard antioxidants, BHA employing DPPH assay and ABTS assay. Fixed reaction time and Steady state measurement were used for study. IC50 and EC50 were calculated. Structure-activity relationship revealed that the electron donating group in the phenolic ring increases the activity where as the electron withdrawing moiety decreases the activity. The Schiff base derivatives showed antioxidant property by two different pathways namely SPLET and HAT mechanisms in DPPH assay. While in ABTS method, the reaction between ABTS radical and Schiff bases involves electron transfer followed by proton transfer (ET-PT) mechanism. The cytotoxicity of these compounds has been evaluated by MTT assay. The results showed that all these compounds are non toxic in nature.

A rhenium complex doped in a silica molecular sieve for molecular oxygen sensing: Construction and characterization.

PubMed

Yang, Xiaozhou; Li, Yanxiao

2016-01-15

This paper reported a diamine ligand and its Re(I) complex for potential application in oxygen sensing. The novelty of this diamine ligand localized at its increased conjugation chain which had a typical electron-withdrawing group of 1,3,4-oxadiazole. Electronic distribution of excited electrons and their lifetime were supposed to be increased, favoring oxygen sensing collision. This hypothesis was confirmed by single crystal analysis, theoretical calculation and photophysical measurement. It was found that this Re(I) complex had a long-lived emission peaking at 545 nm, favoring sensing application. By doping this complex into a silica matrix MCM-41, oxygen sensing performance and mechanism of the resulting composites were discussed in detail. Non-linear Stern-Volmer working curves were observed with maximum sensitivity of 5.54 and short response time of ~6 s. Copyright © 2015 Elsevier B.V. All rights reserved.

25 CFR 1200.13 - How does a tribe apply to withdraw funds?

Code of Federal Regulations, 2013 CFR

2013-04-01

... 25 Indians 2 2013-04-01 2013-04-01 false How does a tribe apply to withdraw funds? 1200.13 Section... INDIAN TRUST FUND MANAGEMENT REFORM ACT Withdrawing Tribal Funds From Trust § 1200.13 How does a tribe apply to withdraw funds? To withdraw funds, a tribe must submit four copies of its application and the...

Estimated Water Use in Puerto Rico, 2005

USGS Publications Warehouse

Molina-Rivera, Wanda L.; Gómez-Gómez, Fernando

2008-01-01

Water-use data were compiled for the 78 municipios of the Commonwealth of Puerto Rico for 2005. Five offstream categories were considered: public-supply water withdrawals and deliveries, domestic self-supplied water use, industrial self-supplied ground-water withdrawals, crop irrigation water use, and thermoelectric power freshwater use. One water-use category also was considered: power-generation instream water use (thermoelectric-saline withdrawals and hydroelectric power). Freshwater withdrawals and deliveries for offstream use from surface- and ground-water sources in Puerto Rico were estimated at 712 million gallons per day (Mgal/d). The largest amount of freshwater withdrawn was by public-supply water facilities and was estimated at 652 Mgal/d. The public-supply domestic water use was estimated at 347 Mgal/d. Fresh surface- and ground-water withdrawals by domestic self-supplied users were estimated at 2.1 Mgal/d and the industrial self-supplied withdrawals were estimated at 9.4 Mgal/d. Withdrawals for crop irrigation purposes were estimated at 45.2 Mgal/d, or approximately 6.3 percent of all offstream freshwater withdrawals. Instream freshwater withdrawals by hydroelectric facilities were estimated at 568 Mgal/d and saline instream surface-water withdrawals for cooling purposes by thermoelectric-power facilities was estimated at 2,288 Mgal/d.

Engineering of Porphyrin Molecules for Use as Effective Cathode Interfacial Modifiers in Organic Solar Cells of Enhanced Efficiency and Stability.

PubMed

Tountas, Marinos; Verykios, Apostolis; Polydorou, Ermioni; Kaltzoglou, Andreas; Soultati, Anastasia; Balis, Nikolaos; Angaridis, Panagiotis A; Papadakis, Michael; Nikolaou, Vasilis; Auras, Florian; Palilis, Leonidas C; Tsikritzis, Dimitris; Evangelou, Evangelos K; Gardelis, Spyros; Koutsoureli, Matroni; Papaioannou, George; Petsalakis, Ioannis D; Kennou, Stella; Davazoglou, Dimitris; Argitis, Panagiotis; Falaras, Polycarpos; Coutsolelos, Athanassios G; Vasilopoulou, Maria

2018-06-20

In the present work, we effectively modify the TiO 2 electron transport layer of organic solar cells with an inverted architecture using appropriately engineered porphyrin molecules. The results show that the optimized porphyrin modifier bearing two carboxylic acids as the anchoring groups and a triazine electron-withdrawing spacer significantly reduces the work function of TiO 2 , thereby reducing the electron extraction barrier. Moreover, the lower surface energy of the porphyrin-modified substrate results in better physical compatibility between the latter and the photoactive blend. Upon employing porphyrin-modified TiO 2 electron transport layers in PTB7:PC 71 BM-based organic solar cells we obtained an improved average power conversion efficiency up to 8.73%. Importantly, porphyrin modification significantly increased the lifetime of the devices, which retained 80% of their initial efficiency after 500 h of storage in the dark. Because of its simplicity and efficacy, this approach should give tantalizing glimpses and generate an impact into the potential of porphyrins to facilitate electron transfer in organic solar cells and related devices.

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

PubMed Central

Islam, Nasarul; Lone, Irfan H.

2017-01-01

The electronic and nonlinear optical (NLO) properties of octaphyrin derivatives were studied by employing the DFT/TDFT at CAM-B3LYP/6-311++G (2d, 2p) level of the theory. Thiophene, phenyl, methyl and cyano moieties were substituted on the molecular framework of octaphyrin core, in order to observe the change in optoelectronic and nonlinear response of these systems. The frontier molecular orbital studies and values of electron affinity reveals that the studied compounds are stable against the oxygen and moisture present in air. The calculated ionization energies, adiabatic electron affinity and reorganization energy values indicate that octaphyrin derivatives can be employed as effective n-type material for Organic Light Emitting Diodes (OLEDs). This character shows an enhancement with the introduction of an electron withdrawing group in the octaphyrin framework. The polarizability and hyperpolarizability values of octaphyrin derivatives demonstrate that they are good candidates for NLO devices. The nonlinear response of these systems shows enhancement on the introduction of electron donating groups on octaphyrin moiety. However, these claims needs further experimental verification. PMID:28321394

The Anti-(+)-Methamphetamine Monoclonal Antibody mAb7F9 Attenuates Acute (+)-Methamphetamine Effects on Intracranial Self-Stimulation in Rats

PubMed Central

Harris, Andrew C.; LeSage, Mark G.; Shelley, David; Perry, Jennifer L.; Pentel, Paul R.; Owens, S. Michael

2015-01-01

Passive immunization with monoclonal antibodies (mAbs) against (+)-methamphetamine (METH) is being evaluated for the treatment of METH addiction. A human/mouse chimeric form of the murine anti-METH mAb7F9 has entered clinical trials. This study examined the effects of murine mAb7F9 on certain addiction-related behavioral effects of METH in rats as measured using intracranial self-stimulation (ICSS). Initial studies indicated that acute METH (0.1-0.56 mg/kg, s.c.) lowered the minimal (threshold) stimulation intensity that maintained ICSS. METH (0.3 mg/kg, s.c.) also blocked elevations in ICSS thresholds (anhedonia-like behavior) during spontaneous withdrawal from a chronic METH infusion (10 mg/kg/day x 7 days). In studies examining effects of i.v. pretreatment with mAb7F9 (at 30, 100, or 200 mg/kg), 200 mg/kg blocked the ability of an initial injection of METH (0.3 mg/kg, s.c.) to reduce baseline ICSS thresholds, but was less capable of attenuating the effect of subsequent daily injections of METH. MAb7F9 (200 mg/kg) also produced a small but significant reduction in the ability of METH (0.3 mg/kg, s.c.) to reverse METH withdrawal-induced elevations in ICSS thresholds. These studies demonstrate that mAb7F9 can partially attenuate some addiction-related effects of acute METH in an ICSS model, and provide some support for the therapeutic potential of mAb7F9 for the treatment of METH addiction. PMID:25742165

Five-year survey of medical student attrition in a medical school in Nigeria: a pilot study.

PubMed

Egwu, Ogugua A; Anyanwu, Godson E

2010-01-01

Student attrition represents a waste of career opportunity and, at times, results in a holistic loss of sense of self-worth for the students involved. The aim of this study was to evaluate the nature, causes, and impact of medical student attrition in Nigeria. A pilot analysis was undertaken using the records of students who failed at medical school as a result of inability to pass the second MBBS examination at Ebonyi State University, Abakaliki, Nigeria, between 2002 and 2007. Some of these students were interviewed using a structured questionnaire. Data analysis showed that 58 (7.8%) of the students admitted into preclinical class withdrew from their study. Thirty-six (62.1%) were males and the rest were females. Thirteen of those withdrawn were interviewed, and 53.8% of them believed they had poor academic ability, while 15.4% attributed their withdrawal to family pressure. No record of guidance or counseling session programs was noted for these students either at the point of withdrawal from the faculty and on the choice of a new career path. As a result of the high attrition rate due to low academic ability, efforts should be made to check students for evidence of this at the point of admission to medicine training. Also, more accommodating teaching programs should be encouraged in faculties to accommodate students with such challenges. Good guidance and counseling programs should be encouraged to handle these inevitable cases of attrition when they occur, to avoid the demoralizing low self-esteem that plagues these individuals for the rest of their lives.

Extinction reveals that primary sensory cortex predicts reinforcement outcome

PubMed Central

Bieszczad, Kasia M.; Weinberger, Norman M.

2011-01-01

Primary sensory cortices are traditionally regarded as stimulus analyzers. However, studies of associative learning-induced plasticity in the primary auditory cortex (A1) indicate involvement in learning, memory and other cognitive processes. For example, the area of representation of a tone becomes larger for stronger auditory memories and the magnitude of area gain is proportional to the degree that a tone becomes behaviorally important. Here, we used extinction to investigate whether “behavioral importance” specifically reflects a sound’s ability to predict reinforcement (reward or punishment) vs. to predict any significant change in the meaning of a sound. If the former, then extinction should reverse area gains as the signal no longer predicts reinforcement. Rats (n = 11) were trained to bar-press to a signal tone (5.0 kHz) for water-rewards, to induce signal-specific area gains in A1. After subsequent withdrawal of reward, A1 was mapped to determine representational areas. Signal-specific area gains — estimated from a previously established brain–behavior quantitative function — were reversed, supporting the “reinforcement prediction” hypothesis. Area loss was specific to the signal tone vs. test tones, further indicating that withdrawal of reinforcement, rather than unreinforced tone presentation per se, was responsible for area loss. Importantly, the amount of area loss was correlated with the amount of extinction (r = 0.82, p < 0.01). These findings show that primary sensory cortical representation can encode behavioral importance as a signal’s value to predict reinforcement, and that the number of cells tuned to a stimulus can dictate its ability to command behavior. PMID:22304434

The nitric oxide donor sodium nitroprusside attenuates recognition memory deficits and social withdrawal produced by the NMDA receptor antagonist ketamine and induces anxiolytic-like behaviour in rats.

PubMed

Trevlopoulou, Aikaterini; Touzlatzi, Ntilara; Pitsikas, Nikolaos

2016-03-01

Experimental evidence indicates that the non-competitive N-methyl-D-aspartate (NMDA) receptor antagonist ketamine impairs cognition and can mimic certain aspects of positive and negative symptoms of schizophrenia in rodents. Nitric oxide (NO) is considered as an intracellular messenger in the brain, and its abnormalities have been linked to schizophrenia. The present study was designed to investigate the ability of the NO donor sodium nitroprusside (SNP) to counteract schizophrenia-like behavioural deficits produced by ketamine in rats. The ability of SNP to reverse ketamine-induced memory deficits and social withdrawal were assessed using the novel object recognition task (NORT) and the social interaction test, respectively. Furthermore, since anxiety disorders are noted to occur commonly in schizophrenics, the effects of SNP on anxiety-like behaviour were examined using the light/dark test. Locomotor activity was also assessed as an independent measure of the potential motoric effects of this NO donor. SNP (0.3 and 1 mg/kg) reversed ketamine (3 mg/kg)-induced short-term recognition memory deficits. SNP (1 mg/kg) counteracted the ketamine (8 mg/kg)-induced social isolation in the social interaction test. The anxiolytic-like effects in the light/dark test of SNP (1 mg/kg) cannot be attributed to changes in locomotor activity. Our findings illustrate a functional interaction between the nitrergic and glutamatergic system that may be of relevance for schizophrenia-like behavioural deficits. The data also suggest a role of NO in anxiety.

Nicotine blood levels and short-term smoking reduction with an electronic nicotine delivery system.

PubMed

Nides, Mitchell A; Leischow, Scott J; Bhatter, Meghna; Simmons, Michael

2014-03-01

To evaluate nicotine delivery from the NJOY® King Bold Electronic Nicotine Delivery System (ENDS) and its short-term potential for smoking reduction or cessation. One week of ad libitum use was followed by measurements of plasma nicotine, heart rate, and craving and withdrawal after 12 hours of nicotine abstinence in 25 adult smokers not interested in quitting. After 5 minutes of use, blood nicotine levels increased by a mean of 3.5 ng/mL (p < .001), heart rate increased, and craving was reduced by 55%. Cigarettes per day were reduced by 39% during the test week, and perceptions of use for reduction or cessation were positive. The NJOY® King Bold ENDS delivers nicotine and led to short-term smoking reduction.

Regioselective Formation of (E)-β-Vinylstannanes with a Topologically Controlled Molybdenum-Based Alkyne Hydrostannation Catalyst.

PubMed

Mandla, Kyle A; Moore, Curtis E; Rheingold, Arnold L; Figueroa, Joshua S

2018-06-04

The regioselective formation of (E)-β-vinylstannanes has been a long-standing challenge in transition-metal-catalyzed alkyne hydrostannation. Herein, we report a well-defined molybdenum-based system featuring two encumbering m-terphenyl isocyanides that reliably and efficiently delivers (E)-β-vinylstannanes from a range of terminal and internal alkynes with high regioselectivity. The system is particularly effective for aryl alkynes and can discriminate between alkyl chains of low steric hindrance in unsymmetrically substituted dialkyl alkynes. Catalytic hydrostannation with this system is also characterized by an electronic effect that leads to a decrease in regioselectivity when electron-withdrawing groups are present on the alkyne substrate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Substituent Effects on π-type Pnicogen Bond Interaction

NASA Astrophysics Data System (ADS)

Zhu, Jian-Qing; Cao, Sheng-Wei; Wang, Wei; Xu, Xiao-Lu; Xu, Hui-Ying

2017-05-01

Intermolecular interactions between PH2Cl and Ar-R (R=H, OH, NH2, CH3, Br, Cl, F, CN, NO2) were calculated by using MP2/aug-cc-pVDZ quantum chemical method. It has been shown from our calculations that the aromatic rings with electron-withdrawing groups represent much weaker binding affinities than those with electron-donating groups. The charge-transfer interaction between PH2Cl and Ar-R plays an important role in the formation of pnicogen bond complexes, as revealed by NBO analysis. The π-type halogen bond was also calculated and comparison of these two π-type interactions was made. It has been revealed that the π-type pnicogen bond systems are more stable than the halogen bond ones.

A new synthetic approach to functionalize pyrimido[4,5-b]quinoline-2,4(1H,3H)-diones via a three-component one-pot reaction.

PubMed

Aknin, Karen; Desbène-Finck, Stéphanie; Helissey, Philippe; Giorgi-Renault, Sylviane

2010-02-01

Functionalized pyrimido[4,5-b]quinoline-2,4 (1H,3H)-diones were synthesized by a three-component one-pot reaction involving barbituric acid, aldehydes, and anilines. The use of commercially available anilines allowed the facile syntheses of pyrimido[4,5-b]quinolinediones substituted in all the positions on the benzene ring with electron donor or electron withdrawing groups. This straightforward method circumvents the preparation of unstable substituted 2-aminobenzaldehydes that limits the scope of previously described syntheses. Furthermore, access to the 5-substituted derivatives is now also possible starting from aliphatic or aromatic aldehydes. Our strategy and methodology offer significant and practical improvements over other methodologies.

Thiazoloisoindigo: a Building Block that Merges the Merits of Thienoisoindigo and Diazaisoindigo for Conjugated Polymers.

PubMed

Wan, Xiaobo; Li, Chenchen; Wang, Xiao; Hio-Ieng, Un; Peng, Jiawei; Lan, Zhenggang; Cai, Mian; Pei, Jian; Wang, Jieyu

2018-04-24

Thiazoloisoindigo, a novel structural variation of isoindigo, is for the first time utilized to synthesize conjugated polymers. Polymer based on thiazoloisoindigo merges the advantages of the one based on thienoisoindigo and diazaisoindigo: It not only exhibits a greatly red shifted UV-vis absorption to the near-infrared region due to its strong tendency to form quinoidal structures, similar to that based on thienoisoindigo, but also shows excellent ambipolar mobility (hole 3.93 and electron 1.07 cm2 V-1 s-1, respectively) in organic field-effect transistors (OFETs), superior than that based on diazaisoindigo, showing the strong electron-withdrawing capability of thiazoloisoindigo. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of functional groups on reduction and activation of quinone bioreductive agents by DT-diaphorase.

PubMed

Fourie, Jeanne; Oleschuk, Curtis J; Guziec, Frank; Guziec, Lynn; Fiterman, Derek J; Monterrosa, Cielo; Begleiter, Asher

2002-02-01

Bioreductive antitumor agents are an important class of anticancer drugs that include the clinically used drug, mitomycin C, and new agents such as EO9 and tirapazamine that have recently been tested in clinical trials. These agents require activation by reductive enzymes such as DT-diaphorase or NADPH:cytochrome P450 reductase. A major focus for improving cancer chemotherapy has been to increase the selectivity and targeting of antitumor drugs to tumor cells. Bioreductive antitumor agents are ideally suited to improving tumor selectivity by an enzyme-directed approach to tumor targeting. However, none of the bioreductive agents developed to date has been specific for activation by a single reductive enzyme. This is in part due to a lack of knowledge about structural factors that confer selectivity for activation by reductive enzymes. The purpose of this study was to investigate the ability of specific functional groups to modify reduction and activation of quinone bioreductive agents by DT-diaphorase. We used a series of model benzoquinone mustard (BM) bioreductive agents and compared the parent compound BM to MBM, which has a strong electron-donating methoxy group, MeBM, which has a weaker electron-donating methyl group, CBM, which has an electron-withdrawing chloro group, and PBM and its structural isomer, meta-PBM (m-PBM), which both have sterically bulky benzene rings attached to the quinone moiety. We determined the rate of reduction of these agents by purified human DT-diaphorase under hypoxic and aerobic conditions. We also measured the cytotoxic activity of these agents in human tumor cell lines with and without the DT-diaphorase inhibitor, dicoumarol. Under hypoxic conditions in vitro, the t(1/2) values for reduction of the analogs by purified DT-diaphorase were 4, 6, 8, 9, 10 and 21 min for BM, MeBM, CBM, MBM, PBM and m-PBM, respectively. Under aerobic conditions the rank order of redox cycling after two-electron reduction by DT-diaphorase was MBM > MeBM > BM approximately CBM approximately PBM approximately m-PBM. The rate of reduction by DT-diaphorase of HBM, a non-alkylating analog of BM, was similar to that of BM under hypoxic conditions, and the rate of redox cycling under aerobic conditions was comparable to that of BM, suggesting that structural changes to the cytotoxic group of these BMs do not affect DT-diaphorase-mediated reduction and redox cycling potential. MBM, MeBM and PBM were more toxic than BM in the NCI-H661 human non-small-cell lung cancer cells and SK-MEL-28 human melanoma cells, while CBM displayed significantly increased cytotoxic activity compared to BM only in the NCI H661 cells. m-PBM had similar cytotoxic activity compared with BM in both cell lines. These cell lines have moderate to high levels of DT-diaphorase activity. When cells were pretreated with the DT-diaphorase inhibitor, dicoumarol, the cytotoxic activity of BM increased while that of MBM decreased in both cell lines, suggesting that BM was inactivated by DT-diaphorase while MBM was activated by this enzyme. Pretreatment of the SK-MEL-28 melanoma cells with dicoumarol resulted in an increased cytotoxic activity of MeBM, but pretreatment of the NCI-H661 cells did not affect the cytotoxicity of MeBM. This suggests, that similar to the results with BM, DT-diaphorase is an inactivating enzyme for MeBM in the SK-MEL-28 cell line. Dicoumarol had no significant effect on the cytotoxicity of CBM, PBM or m-PBM in both cell lines. These studies demonstrated that functional groups can significantly affect the reduction and activation of bioreductive agents by DT-diaphorase. All the functional groups decreased the rate of reduction of the quinone group by DT-diaphorase. Since MeBM and MBM, with electron-donating functional groups, and CBM with an electron-withdrawing functional group had similar half-lives of reduction by DT-diaphorase, steric rather than electronic effects of the functional groups appear to be more important for modifying the rate of reduction by DT-diaphorase. Steric effects on reduction by DT-diaphorase were also influenced by the position of the functional group on the quinone ring moiety, as the reduction of m-PBM was much slower than the reduction of PBM. The electron-donating methoxy and methyl functional groups increased the ability of the reduced products of MBM and MeBM to undergo redox cycling. DT-diaphorase appeared to be an activating enzyme for MBM. This may have resulted in part from increased formation of reactive oxygen species resulting from the increased redox cycling by MBM. In contrast, DT-diaphorase was an inactivating enzyme for BM, and for MeBM in the SK-MEL-28 melanoma cells, possibly because the hydroquinone product of BM and MeBM may be less cytotoxic than the semiquinone produced by one-electron reduction by NADPH:cytochrome P450 reductase.

The Behavioral Effects of a Mixed Efficacy Antinociceptive Peptide, VRP26, Following Chronic Administration in Mice

PubMed Central

Anand, Jessica P.; Boyer, Brett T.; Mosberg, Henry I.; Jutkiewicz, Emily M.

2016-01-01

Rationale VRP26 displays mu opioid receptor agonist and delta opioid receptor antagonist activity in vitro, a pharmacological profile purported to produce reduced tolerance, dependence, and rewarding effects. We hypothesized that VRP26 would display reduced adverse effects after chronic administration as compared with the traditional opioid analgesic fentanyl. Objective To explore the development of tolerance, dependence and conditioned place preference of VRP26 as compared with the traditional opioid analgesic fentanyl. Methods The antinociceptive effects of VRP26 and fentanyl were assessed using the mouse warm water tail withdrawal (WWTW) assay. Measurement of antinociceptive tolerance and physical dependence occurred after seven days of continuous administration of either fentanyl (0.3 mg/kg/day) or VRP26 (10 mg/kg/day); tolerance was measured by a shift in the antinociceptive dose response curve in the WWTW assay. Physical dependence was determined by observation of withdrawal symptoms after precipitated withdrawal. Rewarding effects were measured by the ability of VRP26 or fentanyl to produce conditioned place preference. Results Fentanyl produced significant tolerance and dependence, as well as significant conditioned place preference. VRP26 produced neither tolerance nor physical dependence, nor did it produce significant conditioned place preference. Conclusions These results suggest that chronic treatment with VRP26 may produce less tolerance or physical dependence than chronic treatment with clinically available mu opioid analgesics such as fentanyl. Additionally, VRP26 produces less rewarding effects than fentanyl. This desirable in vivo profile may be due to the mixed efficacy nature of VRP26 and could provide the framework for safer opioid analgesics. PMID:27117141

Introducing the GASP scale: a new measure of guilt and shame proneness.

PubMed

Cohen, Taya R; Wolf, Scott T; Panter, A T; Insko, Chester A

2011-05-01

Although scholars agree that moral emotions are critical for deterring unethical and antisocial behavior, there is disagreement about how 2 prototypical moral emotions--guilt and shame--should be defined, differentiated, and measured. We addressed these issues by developing a new assessment--the Guilt and Shame Proneness scale (GASP)--that measures individual differences in the propensity to experience guilt and shame across a range of personal transgressions. The GASP contains 2 guilt subscales that assess negative behavior-evaluations and repair action tendencies following private transgressions and 2 shame subscales that assess negative self-evaluations (NSEs) and withdrawal action tendencies following publically exposed transgressions. Both guilt subscales were highly correlated with one another and negatively correlated with unethical decision making. Although both shame subscales were associated with relatively poor psychological functioning (e.g., neuroticism, personal distress, low self-esteem), they were only weakly correlated with one another, and their relationships with unethical decision making diverged. Whereas shame-NSE constrained unethical decision making, shame-withdraw did not. Our findings suggest that differentiating the tendency to make NSEs following publically exposed transgressions from the tendency to hide or withdraw from public view is critically important for understanding and measuring dispositional shame proneness. The GASP's ability to distinguish these 2 classes of responses represents an important advantage of the scale over existing assessments. Although further validation research is required, the present studies are promising in that they suggest the GASP has the potential to be an important measurement tool for detecting individuals susceptible to corruption and unethical behavior. (c) 2011 APA, all rights reserved.

The environmental cost of a reference withdrawal from surface waters: Definition and geography

NASA Astrophysics Data System (ADS)

Soligno, Irene; Ridolfi, Luca; Laio, Francesco

2017-12-01

World freshwater ecosystems are significantly deteriorating at a faster rate than other ecosystems. Water withdrawals are recognized as one of the main drivers of growing water stress in river basins worldwide. Over the years, much effort has been devoted to quantify water withdrawals at a global scale; however, comparisons are not simple because the uneven spatiotemporal distribution of surface water resources entails that the same amount of consumed water does not have the same environmental cost in different times or places. In order to account for this spatiotemporal heterogeneity, this work proposes a novel index to assess the environmental cost of a withdrawal from a generic river section. The index depends on (i) the environmental relevance of the impacted fluvial ecosystem (e.g., bed-load transport capacity, width of the riparian belt, biodiversity richness) and (ii) the downstream river network affected by the water withdrawal. The environmental cost has been estimated in each and every river section worldwide considering a reference withdrawal. Being referred to a unitary reference withdrawal that can occur in any river section worldwide, our results can be suitably arranged for describing any scenario of surface water consumption (i.e., as the superposition of the actual pattern of withdrawals). The index aims to support the interpretation of the volumetric measure of surface water withdrawal with a perspective that takes into account the fluvial system where the withdrawal actually occurs. The application of the index highlights the river regions where withdrawals can cause higher environmental costs, with the challenge of weighting each water withdrawal considering the responsibilities that it has on downstream freshwater ecosystems.

Time-dependent negative reinforcement of ethanol intake by alleviation of acute withdrawal

PubMed Central

Cunningham, Christopher L.; Fidler, Tara L.; Murphy, Kevin V.; Mulgrew, Jennifer A.; Smitasin, Phoebe J.

2012-01-01

Background Drinking to alleviate the symptoms of acute withdrawal is included in diagnostic criteria for alcoholism, but the contribution of acute withdrawal relief to high alcohol intake has been difficult to model in animals. Methods Ethanol dependence was induced by passive intragastric ethanol infusions in C57BL/6J (B6) and DBA/2J (D2) mice; non-dependent controls received water infusions. Mice were then allowed to self-administer ethanol or water intragastrically. Results The time course of acute withdrawal was similar to that produced by chronic ethanol vapor exposure in mice, reaching a peak at 7-9 h and returning to baseline within 24 h; withdrawal severity was greater in D2 than in B6 mice (Exp. 1). Post-withdrawal delays in initial ethanol access (1, 3 or 5 days) reduced the enhancement in later ethanol intake normally seen in D2 (but not B6) mice allowed to self-infuse ethanol during acute withdrawal (Exp. 2). The post-withdrawal enhancement of ethanol intake persisted over a 5-d abstinence period in D2 mice (Exp. 3). D2 mice allowed to drink ethanol during acute withdrawal drank more ethanol and self-infused more ethanol than non-dependent mice (Exp. 4). Conclusions Alcohol access during acute withdrawal increased later alcohol intake in a time-dependent manner, an effect that may be related to a genetic difference in sensitivity to acute withdrawal. This promising model of negative reinforcement encourages additional research on the mechanisms underlying acute withdrawal relief and its role in determining risk for alcoholism. PMID:22999529

Ibogaine interferes with motivational and somatic effects of naloxone-precipitated withdrawal from acutely administered morphine.

PubMed

Parke, Linda A; Burton, Page; McDonald, Robert V; Kim, Joseph A; Siegel, Shepard

2002-02-01

It has been reported that ibogaine interferes with somatic withdrawal reactions in rats chronically treated with morphine. The present experiments demonstrated that ibogaine also interferes with motivational withdrawal reactions and somatic withdrawal reactions in rats treated with morphine on only two occasions. On each of two conditioning trials, naloxone was administered 24 h following an injection of morphine. Four hours prior to each naloxone administration, rats were injected with either ibogaine or saline. In two experiments, ibogaine interfered with naloxone-precipitated withdrawal. In Experiment 1, ibogaine-treated rats displayed a weaker aversion to the withdrawal-paired chamber, and in Experiment 2, ibogaine-treated rats displayed fewer somatic withdrawal reactions than did saline treated rats.

Treatment for amphetamine withdrawal.

PubMed

Shoptaw, Steven J; Kao, Uyen; Heinzerling, Keith; Ling, Walter

2009-04-15

Few studies examined treatments for amphetamine withdrawal, although it is a common problem among amphetamine users. Its symptoms, in particular intense craving, may be a critical factor leading to relapse to amphetamine use. In clinical practice, medications for cocaine withdrawal are commonly used to manage amphetamine withdrawal although the pharmacodynamic and pharmacokinetic properties of these two illicit substances are different. To assess the effectiveness of pharmacological alone or in combination with psychosocial treatment for amphetamine withdrawals on discontinuation rates, global state, withdrawal symptoms, craving, and other outcomes. MEDLINE (1966 - 2008), CINAHL (1982 - 2008), PsycINFO (1806 - 2008), CENTRAL (Cochrane Library 2008 issue 2), references of obtained articles. All randomised controlled and clinical trials evaluating pharmacological and or psychosocial treatments (alone or combined) for people with amphetamine withdrawal symptoms. Two authors evaluated and extracted data independently. The data were extracted from intention-to-treat analyses. The Relative Risk (RR) with the 95% confidence interval (95% CI) was used to assess dichotomous outcomes. The Weighted Mean Difference (WMD) with 95% CI was used to assess continuous outcomes. Four randomised controlled trials (involving 125 participants) met the inclusion criteria for the review. Two studies found that amineptine significantly reduced discontinuation rates and improved overall clinical presentation, but did not reduce withdrawal symptoms or craving compared to placebo. The benefits of mirtazapine over placebo for reducing amphetamine withdrawal symptoms were not as clear. One study suggested that mirtazapine may reduce hyperarousal and anxiety symptoms associated with amphetamine withdrawal. A more recent study failed to find any benefit of mirtazapine over placebo on retention or on amphetamine withdrawal symptoms. No medication is effective for treatment of amphetamine withdrawal. Amineptine showed reduction in discontinuation rates and improvement in clinical presentation compared to placebo, but had no effect on reducing withdrawal symptoms or craving. In spite of these limited benefits, amineptine is not available for use due to concerns over abuse liability when using the drug. The benefits of mirtazapine as a withdrawal agent are less clear based on findings from two randomised controlled trials: one report showed improvements in amphetamine withdrawal symptoms over placebo; a second report showed no differences in withdrawal symptoms compared to placebo. Further potential treatment studies should examine medications that increase central nervous system activity involving dopamine, norepinephrine and/or serotonin neurotransmitters, including mirtazapine.

Electronic tools for infectious diseases and microbiology

PubMed Central

Burdette, Steven D

2007-01-01

Electronic tools for infectious diseases and medical microbiology have the ability to change the way the diagnosis and treatment of infectious diseases are approached. Medical information today has the ability to be dynamic, keeping up with the latest research or clinical issues, instead of being static and years behind, as many textbooks are. The ability to rapidly disseminate information around the world opens up the possibility of communicating with people thousands of miles away to quickly and efficiently learn about emerging infections. Electronic tools have expanded beyond the desktop computer and the Internet, and now include personal digital assistants and other portable devices such as cellular phones. These pocket-sized devices have the ability to provide access to clinical information at the point of care. New electronic tools include e-mail listservs, electronic drug databases and search engines that allow focused clinical questions. The goal of the present article is to provide an overview of how electronic tools can impact infectious diseases and microbiology, while providing links and resources to allow users to maximize their efficiency in accessing this information. Links to the mentioned Web sites and programs are provided along with other useful electronic tools. PMID:18978984

Evaluating Distal and Proximal Explanations for Withdrawal: A Rejoinder to Varnum and Kwon's "The Ecology of Withdrawal".

PubMed

Norasakkunkit, Vinai; Uchida, Yukiko; Takemura, Kosuke

2017-01-01

In their 2016 commentary on our theorizing about how youth withdrawal from economic and social participation in Japanese society (i.e., NEET and Hikikomori phenomena) stems from generational inequality of economic opportunities, Varnum and Kwon correctly point out that our explanation for withdrawal is yet untested. They then offered an alternative, evolutionary psychological explanation for withdrawal in which they claim that in resource-rich ecologies like Japan, the option to withdraw from participating in society is a possible life strategy, a strategy that would be much more costly in resource-poor ecologies. While we agree with this premise, we argue that this distal explanatory framework, at least in its current form, has limits in reconciling some of the more recent cross-cultural observations, as well as well-established sociological claims about the causes of withdrawal. Thus we argue that much work remains in refining and expanding the explanatory power of more distal explanations on the issue of withdrawal. Until then, the more proximal and culture-specific explanations are probably the useful and meaningful explanations for the withdrawal phenomenon.

Withdrawal of anticancer therapy in advanced disease: a systematic literature review.

PubMed

Clarke, G; Johnston, S; Corrie, P; Kuhn, I; Barclay, S

2015-11-11

Current guidelines set out when to start anticancer treatments, but not when to stop as the end of life approaches. Conventional cytotoxic agents are administered intravenously and have major life-threatening toxicities. Newer drugs include molecular targeted agents (MTAs), in particular, small molecule kinase-inhibitors (KIs), which are administered orally. These have fewer life-threatening toxicities, and are increasingly used to palliate advanced cancer, generally offering additional months of survival benefit. MTAs are substantially more expensive, between £2-8 K per month, and perceived as easier to start than stop. A systematic review of decision-making concerning the withdrawal of anticancer drugs towards the end of life within clinical practice, with a particular focus on MTAs. Nine electronic databases searched. PRISMA guidelines followed. Forty-two studies included. How are decisions made? Decision-making was shared and ongoing, including stopping, starting and trying different treatments. Oncologists often experienced 'professional role dissonance' between their self-perception as 'treaters', and talking about end of life care. Why are decisions made? Clinical factors: disease progression, worsening functional status, treatment side-effects. Non-clinical factors: physicians' personal experience, values, emotions. Some patients continued treatment to maintain 'hope', often reflecting limited understanding of palliative goals. When are decisions made? Limited evidence reveals patients' decisions based upon quality of life benefits. Clinicians found timing withdrawal particularly challenging. Who makes the decisions? Decisions were based within physician-patient interaction. Oncologists report that decisions around stopping chemotherapy treatment are challenging, with limited evidence-based guidance outside of clinical trial protocols. The increasing availability of oral MTAs is transforming the management of incurable cancer; blurring boundaries between active treatment and palliative care. No studies specifically addressing decision-making around stopping MTAs in clinical practice were identified. There is a need to develop an evidence base to support physicians and patients with decision-making around the withdrawal of these high cost treatments.

Uncertainties from a worldwide survey on antiepileptic drug withdrawal after seizure remission.

PubMed

Bartolini, Luca; Majidi, Shahram; Koubeissi, Mohamad Z

2018-04-01

We sought to determine differences in practice for discontinuation of antiepileptic drugs (AEDs) after seizure remission and stimulate the planning and conduction of withdrawal trials. We utilized a worldwide electronic survey that included questions about AED discontinuation for 3 paradigmatic cases in remission: (1) focal epilepsy of unknown etiology, (2) temporal lobe epilepsy after surgery, and (3) juvenile myoclonic epilepsy. We analyzed 466 complete questionnaires from 53 countries, including the United States. Statistical analysis included χ 2 and multivariate logistic regression. Case 1: responders in practice for <10 years were less likely to taper AEDs: odds ratio (OR) (95% confidence interval [CI]) 0.52 (0.32-0.85), p = 0.02. The likelihood of stopping AEDs was higher among doctors treating children: OR (95% CI): 11.41 (2.51-40.13), p = 0.002. Doctors treating children were also more likely to stop after 2 years or less of remission: OR (95% CI): 6.91 (2.62-19.31), p = 0.002, and the same was observed for US physicians: OR (95% CI): 1.61 (1.01-2.57), p = 0.0049. Case 2: responders treating children were more likely to taper after 1 year or less of postoperative remission, with the goal of discontinuing all medications: OR (95% CI): 1.91 (1.09-3.12), p = 0.015, and so were US-based responders: OR (95% CI): 1.73 (1.21-2.41), p = 0.003. Case 3: epileptologists were less likely to withdraw the medication: OR (95% CI): 0.56 (0.39-0.82), p = 0.003, and so were those in practice for 10 or more years: OR (95% CI): 0.54 (0.31-0.95), p = 0.025. We observed several differences in practice for AED withdrawal after seizure remission that highlight global uncertainty. Trials of AED discontinuation are needed to provide evidence-based guidance.

Efficacy and safety of interleukin-1 antagonists in rheumatoid arthritis: a systematic review and meta-analysis.

PubMed

Nikfar, Shekoufeh; Saiyarsarai, Parisa; Tigabu, Bereket Molla; Abdollahi, Mohammad

2018-05-08

Rheumatoid arthritis patients have a high level of pro-inflammatory interleukin-1. Augmenting the blockade of interleukin-1 receptors by external interleukin-1 receptor antagonist modifies the progression of the disease. Therefore, the aim of this study was to evaluate the clinical efficacy and safety of interleukin-1 receptor antagonist (anakinra) in the treatment of rheumatoid arthritis. Clinical trials and extension studies that compared anakinra with placebo or other medications were included. Electronic bibliographic databases: PubMed, Scopus, and Web of Sciences were searched from inception to November 2017. The American College of Rheumatology 20% (ACR20) improvement was the primary efficacy outcome measure. Total number of adverse drug events, serious adverse drug events, total treatment withdrawals, and treatment-related withdrawals were safety outcome measures. Ten studies were included in this review. One study did not fulfil quantitative criteria and was assessed qualitatively. Six clinical trials and three extension studies were included in meta-analysis. Patients treated with anakinra are 42% more likely to have ACR20 response than patients without IL-1Ra (pooled RR 1.42; 95% CI 1.01, 2.00). Patients on 30-150 mg anakinra have lower Health Assessment Questionnaire (HAQ) score than patients without IL-1Ra (SMD - 0.28; 95% CI - 0.53, - 0.03). The inflammatory marker erythrocyte sedimentation rate (ESR) was significantly lower among patients treated with 30-150 mg anakinra (SMD - 0.44; 95% CI - 0.65, - 0.23). Patients on anakinra have a 34% more risk of treatment-related withdrawal than placebo. The other parameters were not found to be statistically significant. Anakinra has a significant improvement in ACR20, HAQ, and ESR. The ACR20 response is maintained after 48 weeks of treatment. Anakinra shows higher episodes of treatment-related withdrawals than placebo.

New York Water-Use Program and data, 2000

USGS Publications Warehouse

Lumia, Deborah S.; Linsey, Kristin S.

2005-01-01

New York ranked third after California and Texas in withdrawals of freshwater for public supply, in the withdrawal of fresh surface water for public-water supply, in total population, and in number of people served by public-water supplies. New York ranked sixth in total withdrawals for the generation of thermoelectric power and total surface-water withdrawals. Finally, New York ranked fourth in withdrawals of ground water for public supply.

Topiramate in opiate withdrawal.

PubMed

Zullino, Daniele F; Cottier, Anne-Claude; Besson, Jacques

2002-10-01

The alpha2-adrenergic agonist clonidine is the mainly used drug for the opiate withdrawal. Its efficacy and tolerance in treating withdrawal symptoms is, however, suboptimal. The pharmacological profile of topiramate suggests it could be rather valuable for opiate withdrawal, as there is some evidence that topiramate acts, among others, through inhibition of alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors, which play an important role in the withdrawal-induced activation of the locus coeruleus (LC) by glutamate. Three patients undergoing an inpatient opiate detoxification program were treated with topiramate, which achieved a nearly complete control of withdrawal symptoms.

Withdrawal symptoms in internet gaming disorder: A systematic review.

PubMed

Kaptsis, Dean; King, Daniel L; Delfabbro, Paul H; Gradisar, Michael

2016-02-01

Internet gaming disorder (IGD) is currently positioned in the appendix of the DSM-5 as a condition requiring further study. The aim of this review was to examine the state of current knowledge of gaming withdrawal symptomatology, given the importance of withdrawal in positioning the disorder as a behavioral addiction. A total of 34 studies, including 10 qualitative studies, 17 research reports on psychometric instruments, and 7 treatment studies, were evaluated. The results indicated that the available evidence on Internet gaming withdrawal is very underdeveloped. Internet gaming withdrawal is most consistently referred to as 'irritability' and 'restlessness' following cessation of the activity. There exists a concerning paucity of qualitative studies that provide detailed clinical descriptions of symptoms arising from cessation of internet gaming. This has arguably compromised efforts to quantify withdrawal symptoms in empirical studies of gaming populations. Treatment studies have not reported on the natural course of withdrawal and/or withdrawal symptom trajectory following intervention. It is concluded that many more qualitative clinical studies are needed, and should be prioritised, to develop our understanding of gaming withdrawal. This should improve clinical descriptions of problematic internet gaming and in turn improve the quantification of IGD withdrawal and thus treatments for harmful internet gaming. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of the Phosphine Steric and Electronic Profile on the Rh-Promoted Dehydrocoupling of Phosphine–Boranes

PubMed Central

2014-01-01

The electronic and steric effects in the stoichiometric dehydrocoupling of secondary and primary phosphine–boranes H3B·PR2H [R = 3,5-(CF3)2C6H3; p-(CF3)C6H4; p-(OMe)C6H4; adamantyl, Ad] and H3B·PCyH2 to form the metal-bound linear diboraphosphines H3B·PR2BH2·PR2H and H3B·PRHBH2·PRH2, respectively, are reported. Reaction of [Rh(L)(η6-FC6H5)][BArF4] [L = Ph2P(CH2)3PPh2, ArF = 3,5-(CF3)2C6H3] with 2 equiv of H3B·PR2H affords [Rh(L)(H)(σ,η-PR2BH3)(η1-H3B·PR2H)][BArF4]. These complexes undergo dehydrocoupling to give the diboraphosphine complexes [Rh(L)(H)(σ,η2-PR2·BH2PR2·BH3)][BArF4]. With electron-withdrawing groups on the phosphine–borane there is the parallel formation of the products of B–P cleavage, [Rh(L)(PR2H)2][BArF4], while with electron-donating groups no parallel product is formed. For the bulky, electron rich, H3B·P(Ad)2H no dehydrocoupling is observed, but an intermediate Rh(I) σ phosphine–borane complex is formed, [Rh(L){η2-H3B·P(Ad)2H}][BArF4], that undergoes B–P bond cleavage to give [Rh(L){η1-H3B·P(Ad)2H}{P(Ad)2H}][BArF4]. The relative rates of dehydrocoupling of H3B·PR2H (R = aryl) show that increasingly electron-withdrawing substituents result in faster dehydrocoupling, but also suffer from the formation of the parallel product resulting from P–B bond cleavage. H3B·PCyH2 undergoes a similar dehydrocoupling process, and gives a mixture of stereoisomers of the resulting metal-bound diboraphosphine that arise from activation of the prochiral P–H bonds, with one stereoisomer favored. This diastereomeric mixture may also be biased by use of a chiral phosphine ligand. The selectivity and efficiencies of resulting catalytic dehydrocoupling processes are also briefly discussed. PMID:24617924

Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: assessment of metallocene conformation from NMR spin couplings and use in palladium-catalyzed chloroarenes activation.

PubMed

Mom, Sophal; Beaupérin, Matthieu; Roy, David; Royer, Sylviane; Amardeil, Régine; Cattey, Hélène; Doucet, Henri; Hierso, J-C

2011-11-21

The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even when electron-rich substituents are present. This set of polyphosphanes displays varied conformational features, which are discussed in the light of their multinuclear NMR characterization in solution and of the X-ray solid state structure of the representative triphosphane 1,2-bis(diphenylphosphanyl)-1'-(diisopropylphosphanyl)-3'-(triphenyl)methyl-4-tert-butyl ferrocene, 11. In particular, the existence of a range of significantly different nonbonded ("through-space", TS) spin-spin coupling constants between heteroannular P atoms, for the triphosphanes of this class, allowed their preferred conformation in solution to be appraised. The study evidences an unanticipated flexibility of the ferrocene platform, despite the presence of very congested tert-butyl and trityl groups. Herein, we show that, contrary to our first belief, the preferred conformation for the backbone of ferrocenyl polyphosphanes can not only depend on the hindrance of the groups decorating the cyclopentadienyl rings but is also a function of the substituents of the phosphanyl groups. The interest of these robust phosphanes as ligands was illustrated in palladium catalysis for the arylation of n-butyl furan with chloroarenes, using direct C-H activation of the heteroaromatic in the presence of low metal/ligand loadings (0.5-1.0 mol %). Thus, 4-chlorobenzonitrile, 4-chloronitrobenzene, 4-chloropropiophenone, and 4-(trifluoromethyl)chlorobenzene were efficiently coupled to n-butyl furan, using Pd(OAc)(2) associated to the new diphosphane ligands 1,1'-bis(diisopropylphosphanyl)-3,3'-di(triphenyl)methyl ferrocene (15) or 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenyl)methylferrocene (16), which respectively hold the electron-rich -Pi-Pr(2) and -PCy(2) groups.

Water Use in Oklahoma 1950-2005

USGS Publications Warehouse

Tortorelli, Robert L.

2009-01-01

Comprehensive planning for water resources development and use in Oklahoma requires a historical perspective on water resources. The U.S. Geological Survey, in cooperation with the Oklahoma Water Resources Board, summarized the 1950-2005 water-use information for Oklahoma. This report presents 1950-2005 estimates of freshwater withdrawal for water use in Oklahoma by source and category in 5-year intervals. Withdrawal source was either surface water or groundwater. Withdrawal categories include: public supply, irrigation, livestock and aquaculture, thermoelectric-power generation (cooling water), domestic and commercial, and industrial and mining. Withdrawal data were aggregated and tabulated by county, major river basin, and principal aquifer. The purpose of this report is to summarize water-use data in Oklahoma through: (1) presentation of detailed information on freshwater withdrawals by source, county, major river basin, and principal aquifer for 2005; (2) comparison of water use by source, category, major river basin, and principal aquifer at 5-year intervals from 1990-2005; and (3) comparison of water use on a statewide basis by source and category at 5-year intervals from 1950-2005. Total withdrawals from surface-water and groundwater sources during 2005 were 1,559 million gallons per day-989 million gallons a day or 63 percent from surface-water sources and 570 million gallons per day or 37 percent from groundwater sources. The three largest water use categories were: public supply, 646 million gallons per day or 41 percent of total withdrawals; irrigation, 495 million gallons per day or 32 percent of total withdrawals; and livestock and aquaculture, 181 million gallons per day or 12 percent of total withdrawals. All other categories were 237 million gallons per day or 15 percent of total withdrawals. The influence of public supply on the total withdrawals can be seen in the eastern two-thirds of Oklahoma; whereas, the influence of irrigation on total withdrawals can be seen in the western third of Oklahoma. Surface-water sources were dominant in the eastern half of Oklahoma and groundwater sources were dominant in the western half of Oklahoma. Public supply withdrawals increased steadily from 1990-2000 and then decreased slightly in 2005, mainly because of a decrease in surface-water withdrawals. Irrigation withdrawals increased from 1990-1995 and then decreased steadily to 2005. Total livestock and aquaculture withdrawals steadily increased from 1990-2005. The largest increase in the other categories was for thermoelectric power generation that has steadily increased and almost doubled from 1990-2005. Surface-water sources have been increasing in importance from 1950-2005, in part because of the increasing percentage of surface-water for public supply as the total population of Oklahoma and population served by surface-water sources increased. Groundwater sources have been generally decreasing in importance as a percentage of total withdrawals in recent years. However, the magnitude of groundwater withdrawals was greatly dependent on irrigation withdrawals and specifically irrigated acreage in the panhandle.

Emergence of dormant conditioned incentive approach by conditioned withdrawal in nicotine addiction.

PubMed

Scott, Daniel; Hiroi, Noboru

2010-10-15

Nicotine is one of the determinants for the development of persistent smoking, and this maladaptive behavior is characterized by many symptoms, including withdrawal and nicotine seeking. The process by which withdrawal affects nicotine seeking is poorly understood. The impact of a withdrawal-associated cue on nicotine (.2 mg/kg)-conditioned place preference was assessed in male C57BL/6J mice (n = 8-17/group). To establish a cue selectively associated with withdrawal distinct from those associated with nicotine, a tone was paired with withdrawal in their home cages; mice were chronically exposed to nicotine (200 μg/mL for 15 days) from drinking water in their home cages and received the nicotinic acetylcholine receptor antagonist mecamylamine (2.5 mg/kg) to precipitate withdrawal in the presence of a tone. The effect of the withdrawal-associated tone on nicotine-conditioned place preference was then evaluated in the place-conditioning apparatus after a delay, when nicotine-conditioned place preference spontaneously disappeared. A cue associated with precipitated withdrawal reactivated the dormant effect of nicotine-associated cues on conditioned place preference. This effect occurred during continuous exposure to nicotine but not during abstinence. A conditioned withdrawal cue could directly amplify the incentive properties of cues associated with nicotine. This observation extends the contemporary incentive account of the role of withdrawal in addiction to cue-cue interaction. Copyright © 2010 Society of Biological Psychiatry. Published by Elsevier Inc. All rights reserved.

5 CFR 362.407 - Withdrawal and readmission.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 5 Administrative Personnel 1 2014-01-01 2014-01-01 false Withdrawal and readmission. 362.407 Section 362.407 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PATHWAYS PROGRAMS Presidential Management Fellows Program § 362.407 Withdrawal and readmission. (a) Withdrawal. (1...

5 CFR 362.407 - Withdrawal and readmission.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 5 Administrative Personnel 1 2013-01-01 2013-01-01 false Withdrawal and readmission. 362.407 Section 362.407 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PATHWAYS PROGRAMS Presidential Management Fellows Program § 362.407 Withdrawal and readmission. (a) Withdrawal. (1...

5 CFR 831.1207 - Withdrawal of disability retirement applications.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 5 Administrative Personnel 2 2010-01-01 2010-01-01 false Withdrawal of disability retirement...) CIVIL SERVICE REGULATIONS (CONTINUED) RETIREMENT Disability Retirement § 831.1207 Withdrawal of... any further consideration. (b) Withdrawal of a disability retirement application does not ensure the...

Trajectories of Social Withdrawal from Grades 1 to 6: Prediction from Early Parenting, Attachment, and Temperament

PubMed Central

Booth-LaForce, Cathryn; Oxford, Monica L.

2015-01-01

From 1092 children in the NICHD Study of Early Child Care and Youth Development, we identified three trajectory patterns of social withdrawal from teacher reports in Grades 1-6: A Normative consistently low group (86%); a Decreasing group (5%) with initially high withdrawal that decreased; and an Increasing group (9%) with initially low withdrawal that increased. Prediction models supported the role of early dysregulated temperament, insensitive parenting, and attachment. Preschool shy temperament was a specific pathway to decreasing withdrawal, and poor inhibitory control, to increasing withdrawal. Children on the increasing pathway were more lonely, solitary, and excluded by peers. Results suggest differentiated pathways to varying trajectories of social withdrawal and highlight the importance of identification of longitudinal patterns in relation to risk. PMID:18793064

Acute opioid withdrawal is associated with increased neural activity in reward-processing centers in healthy men: A functional magnetic resonance imaging study.

PubMed

Chu, Larry F; Lin, Joanne C; Clemenson, Anna; Encisco, Ellen; Sun, John; Hoang, Dan; Alva, Heather; Erlendson, Matthew; Clark, J David; Younger, Jarred W

2015-08-01

Opioid analgesics are frequently prescribed for chronic pain. One expected consequence of long-term opioid use is the development of physical dependence. Although previous resting state functional magnetic resonance imaging (fMRI) studies have demonstrated signal changes in reward-associated areas following morphine administration, the effects of acute withdrawal on the human brain have been less well-investigated. In an earlier study by our laboratory, ondansetron was shown to be effective in preventing symptoms associated with opioid withdrawal. The purpose of this current study was to characterize neural activity associated with acute opioid withdrawal and examine whether these changes are modified by ondansetron. Ten participants were enrolled in this placebo-controlled, randomized, double-blind, crossover study and attended three acute opioid withdrawal sessions. Participants received either placebo or ondansetron (8Ymg IV) before morphine administration (10Ymg/70Ykg IV). Participants then underwent acute naloxone-precipitated withdrawal during a resting state fMRI scan. Objective and subjective opioid withdrawal symptoms were assessed. Imaging results showed that naloxone-precipitated opioid withdrawal was associated with increased neural activity in several reward processing regions, including the right pregenual cingulate, putamen, and bilateral caudate, and decreased neural activity in networks involved in sensorimotor integration. Ondansetron pretreatment did not have a significant effect on the imaging correlates of opioid withdrawal. This study presents a preliminary investigation of the regional changes in neural activity during acute opioid withdrawal. The fMRI acute opioid withdrawal model may serve as a tool for studying opioid dependence and withdrawal in human participants. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

A lack of association between severity of nicotine withdrawal and individual differences in compensatory nicotine self-administration in rats

PubMed Central

Harris, Andrew C.; Pentel, Paul R.; Burroughs, Danielle; Staley, Mylissa D.; LeSage, Mark G.

2013-01-01

Rationale Compensatory smoking may represent an adverse consequence of smoking reduction or the use of reduced nicotine tobacco products. Factors contributing to individual variability in compensation are poorly understood. Objective To examine whether severity of nicotine withdrawal as measured by elevated intracranial self-stimulation (ICSS) thresholds is related to individual differences in compensatory nicotine self-administration (NSA) following unit dose reduction. Methods Rats were trained for ICSS and NSA (0.06 mg/kg/inf). After stabilization, effects of reducing the nicotine unit dose to 0.03 mg/kg/inf were examined. Following reacquisition of NSA (0.06 mg/kg/inf), effects of antagonist-precipitated withdrawal and saline extinction (spontaneous withdrawal) were examined. Results Reducing the NSA unit dose produced partial compensation as indicated by increased infusion rates but a 35% mean decrease in daily nicotine intake. Magnitude of compensation varied considerably among rats. Dose reduction did not elicit withdrawal in rats as a group, although there were substantial increases in ICSS thresholds in some animals. Intracranial self-stimulation thresholds were consistently elevated during precipitated and spontaneous withdrawal, confirming that rats were nicotine-dependent. Individual differences in compensation were not correlated with changes in ICSS thresholds during dose reduction, precipitated withdrawal, or spontaneous withdrawal. In a secondary analysis, greater precipitated withdrawal severity predicted greater initial nicotine-seeking during extinction. Conclusions Severity of nicotine withdrawal was not related to the degree of compensation in this protocol. These data do not support a role for nicotine withdrawal in individual differences in compensation during reduced nicotine exposure, but do suggest that withdrawal may contribute to nicotine-seeking during early abstinence. PMID:21494791

Aggression and increased glutamate in the mPFC during withdrawal from intermittent alcohol in outbred mice.

PubMed

Hwa, Lara S; Nathanson, Anna J; Shimamoto, Akiko; Tayeh, Jillian K; Wilens, Allison R; Holly, Elizabeth N; Newman, Emily L; DeBold, Joseph F; Miczek, Klaus A

2015-08-01

Disrupted social behavior, including occasional aggressive outbursts, is characteristic of withdrawal from long-term alcohol (EtOH) use. Heavy EtOH use and exaggerated responses during withdrawal may be treated using glutamatergic N-methyl-D-aspartate receptor (NMDAR) antagonists. The current experiments explore aggression and medial prefrontal cortex (mPFC) glutamate as consequences of withdrawal from intermittent access to EtOH and changes in aggression and mPFC glutamate caused by NMDAR antagonists memantine and ketamine. Swiss male mice underwent withdrawal following 1-8 weeks of intermittent access to 20 % EtOH. Aggressive and nonaggressive behaviors with a conspecific were measured 6-8 h into EtOH withdrawal after memantine or ketamine (0-30 mg/kg, i.p.) administration. In separate mice, extracellular mPFC glutamate after memantine was measured during withdrawal using in vivo microdialysis. At 6-8 h withdrawal from EtOH, mice exhibited more convulsions and aggression and decreased social contact compared to age-matched water controls. Memantine, but not ketamine, increased withdrawal aggression at the 5-mg/kg dose in mice with a history of 8 weeks of EtOH but not 1 or 4 weeks of EtOH or in water drinkers. Tonic mPFC glutamate was higher during withdrawal after 8 weeks of EtOH compared to 1 week of EtOH or 8 weeks of water. Five milligrams per kilogram of memantine increased glutamate in 8-week EtOH mice, but also in 1-week EtOH and water drinkers. These studies reveal aggressive behavior as a novel symptom of EtOH withdrawal in outbred mice and confirm a role of NMDARs during withdrawal aggression and for disrupted social behavior.

Aggression and increased glutamate in the mPFC during withdrawal from intermittent alcohol in outbred mice

PubMed Central

Hwa, Lara S.; Nathanson, Anna J.; Shimamoto, Akiko; Tayeh, Jillian K.; Wilens, Allison R.; Holly, Elizabeth N.; Newman, Emily L.; DeBold, Joseph F.; Miczek, Klaus A.

2015-01-01

Rationale Disrupted social behavior, including occasional aggressive outbursts, is characteristic of withdrawal from long-term alcohol (EtOH) use. Heavy EtOH use and exaggerated responses during withdrawal may be treated using glutamatergic N-methyl-D-aspartate receptor (NMDAR) antagonists. Objectives The current experiments explore aggression and medial prefrontal cortex (mPFC) glutamate as consequences of withdrawal from intermittent access to EtOH, and changes in aggression and mPFC glutamate caused by NMDAR antagonists memantine and ketamine. Methods Swiss male mice underwent withdrawal following 1-8 weeks of intermittent access to 20% EtOH. Aggressive and non-aggressive behaviors with a conspecific were measured 6-8 h into EtOH withdrawal after memantine or ketamine (0-30 mg/kg, i.p.) administration. In separate mice, extracellular mPFC glutamate after memantine was measured during withdrawal using in vivo microdialysis. Results At 6-8 h withdrawal from EtOH, mice exhibited more convulsions and aggression, and decreased social contact compared to age-matched water controls. Memantine, but not ketamine, increased withdrawal aggression at the 5 mg/kg dose in mice with a history of 8 weeks EtOH but not 1 or 4 weeks of EtOH or in water drinkers. Tonic mPFC glutamate was higher during withdrawal after 8 weeks EtOH compared to 1 week EtOH or 8 weeks water. Five mg/kg memantine increased glutamate in 8 week EtOH mice, but also in 1 week EtOH and water drinkers. Conclusions These studies reveal aggressive behavior as a novel symptom of EtOH withdrawal in outbred mice and confirm a role of NMDARs during withdrawal aggression and for disrupted social behavior. PMID:25899790

Response to CPAP Withdrawal in Patients with Mild Versus Severe Obstructive Sleep Apnea/Hypopnea Syndrome

PubMed Central

Young, Laura R.; Taxin, Zachary H.; Norman, Robert G.; Walsleben, Joyce A.; Rapoport, David M.; Ayappa, Indu

2013-01-01

Background: Patients with obstructive sleep apnea/hypopnea syndrome (OSAHS), even those generally compliant with CPAP therapy, often intermittently discontinue CPAP. Study Objective: Examine the impact of CPAP withdrawal on sleep, sleep disordered breathing (SDB), and daytime function in subjects with varying severity of OSAHS. Patients and Interventions: Forty-two subjects (26M/16 F) with OSAHS (AHI4% = 45.2 ± 35.5/h pretreatment) on CPAP for 4 months were evaluated on the second night of CPAP withdrawal. Sleep architecture, SDB indices, and subjective/objective daytime function were assessed pretreatment, on CPAP therapy, and after CPAP withdrawal. Comparisons were made between pretreatment and CPAP withdrawal for the entire group, and for subgroups of mild/moderate (AHI4% < 30/h, n = 22) and severe (AHI4% > 30/h, n = 20) SDB. Results: Overall, and for mild/moderate subjects, SDB indices returned to pretreatment values on CPAP withdrawal but with fewer apneas and more hypopneas/RERAs. For severe SDB, the event frequency (AI, AHI4%, and RDI) was lower and O2 desaturation was improved on CPAP withdrawal. Across SDB severity, sleep architecture showed lower %REM (15.6% vs 12.9%, P = 0.009) on the CPAP withdrawal compared to pretreatment. Stanford Sleepiness Score, MSLT, and PVT measures were not significantly different between pretreatment and CPAP withdrawal. Conclusions: Over a wide range of SDB severity CPAP withdrawal results in recurrence of SDB, albeit with less severe O2 desaturation. Subjective/objective daytime function returned to pretreatment levels. Sleep architecture changes on CPAP withdrawal (acute SDB) may reflect reduced sleep pressure compared to pretreatment chronic SDB. Our data suggest detrimental effects of even brief withdrawal of CPAP in subjects with both mild and severe OSAHS. Citation: Young LR; Taxin ZH; Norman RG; Walsleben JA; Rapoport DM; Ayappa I. Response to CPAP withdrawal in patients with mild versus severe obstructive sleep apnea/hypopnea syndrome. SLEEP 2013;36(3):405-412. PMID:23449493

21 CFR 870.1800 - Withdrawal-infusion pump.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Withdrawal-infusion pump. 870.1800 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Diagnostic Devices § 870.1800 Withdrawal-infusion pump. (a) Identification. A withdrawal-infusion pump is a device designed to inject accurately drugs...

Electron Microscopic Study of Demyelination in an Experimentally Induced Lesion in Adult Cat Spinal Cord

PubMed Central

Bunge, Richard P.; Bunge, Mary Bartlett; Ris, Hans

1960-01-01

Plaques of subpial demyelination were induced in adult cat spinal cords by repeated withdrawal and reinjection of cerebrospinal fluid. Peripheral cord was fixed by replacing cerebrospinal fluid available at cisternal puncture with 3 per cent buffered OsO4. Following extirpation, surface tissue was further fixed in 2 per cent buffered OsO4, dehydrated in ethanol, and embedded in araldite. Normal subpial cord consists mainly of myelinated axons and two types of macroglia, fibrous astrocytes and oligodendrocytes. Twenty-nine hours after lesion induction most myelin sheaths are deteriorating and typical macroglia are no longer visible. Phagocytosis of myelin debris has begun. In 3-day lesions, axons are intact and their mitochondria and neurofibrils appear normal despite continued myelin breakdown. All axons are completely demyelinated by 6 days. They lack investments only briefly, however, for at 10 and 14 days, macroglial processes appear and embrace them. These macroglia do not resemble either one of the normally occurring glia; their dense cytoplasm contains fibrils in addition to the usual organelles. It is proposed that these macroglia, which later accomplish remyelination, are the hypertrophic or swollen astrocytes of classical neuropathology. The suggestion that these astrocytes possess the potential to remyelinate axons in addition to their known ability to form cicatrix raises the possibility of pharmacological control of their expression. PMID:13805917

Cannabidiol for the treatment of cannabis withdrawal syndrome: a case report.

PubMed

Crippa, J A S; Hallak, J E C; Machado-de-Sousa, J P; Queiroz, R H C; Bergamaschi, M; Chagas, M H N; Zuardi, A W

2013-04-01

  Cannabis withdrawal in heavy users is commonly followed by increased anxiety, insomnia, loss of appetite, migraine, irritability, restlessness and other physical and psychological signs. Tolerance to cannabis and cannabis withdrawal symptoms are believed to be the result of the desensitization of CB1 receptors by THC.   This report describes the case of a 19-year-old woman with cannabis withdrawal syndrome treated with cannabidiol (CBD) for 10 days. Daily symptom assessments demonstrated the absence of significant withdrawal, anxiety and dissociative symptoms during the treatment.   CBD can be effective for the treatment of cannabis withdrawal syndrome. © 2012 Blackwell Publishing Ltd.

Estimated use of water in the United States in 2010

USGS Publications Warehouse

Maupin, Molly A.; Kenny, Joan F.; Hutson, Susan S.; Lovelace, John K.; Barber, Nancy L.; Linsey, Kristin S.

2014-01-01

In 2010, more than 50 percent of the total withdrawals in the United States were accounted for by 12 States. California accounted for about 11 percent of the total withdrawals and 10 percent of freshwater withdrawals in the United States, predominantly for irrigation. Texas accounted for about 7 percent of total withdrawals, predominantly for thermoelectric power, irrigation, and public supply. Florida accounted for 18 percent of the total saline-water withdrawals in the United States, mostly from surface-water sources for thermoelectric power. Oklahoma and Texas accounted for about 70 percent of the total saline groundwater withdrawals in the United States, mostly for mining.

Estimated water use in Puerto Rico, 2010

USGS Publications Warehouse

Molina-Rivera, Wanda L.

2014-01-01

Water-use data were aggregated for the 78 municipios of the Commonwealth of Puerto Rico for 2010. Five major offstream categories were considered: public-supply water withdrawals and deliveries, domestic and industrial self-supplied water use, crop-irrigation water use, and thermoelectric-power freshwater use. One instream water-use category also was compiled: power-generation instream water use (thermoelectric saline withdrawals and hydroelectric power). Freshwater withdrawals for offstream use from surface-water [606 million gallons per day (Mgal/d)] and groundwater (118 Mgal/d) sources in Puerto Rico were estimated at 724 million gallons per day. The largest amount of freshwater withdrawn was by public-supply water facilities estimated at 677 Mgal/d. Public-supply domestic water use was estimated at 206 Mgal/d. Fresh groundwater withdrawals by domestic self-supplied users were estimated at 2.41 Mgal/d. Industrial self-supplied withdrawals were estimated at 4.30 Mgal/d. Withdrawals for crop irrigation purposes were estimated at 38.2 Mgal/d, or approximately 5 percent of all offstream freshwater withdrawals. Instream freshwater withdrawals by hydroelectric facilities were estimated at 556 Mgal/d and saline instream surface-water withdrawals for cooling purposes by thermoelectric-power facilities was estimated at 2,262 Mgal/d.

Increased QT interval variability index in acute alcohol withdrawal.

PubMed

Bär, Karl-Jürgen; Boettger, Michael Karl; Koschke, Mandy; Boettger, Silke; Grotelüschen, Marei; Voss, Andreas; Yeragani, Vikram K

2007-07-10

Acute alcohol withdrawal is associated with increased cardiovascular mortality, most likely due to cardiac arrhythmias. As the QT interval reflects the most critical phase for the generation of reentry and thus for arrhythmia, we examined QT variability in patients suffering from acute alcohol withdrawal. High resolution electrocardiographic recordings were performed in 18 male unmedicated patients suffering from acute alcohol withdrawal, 18 matched controls and 15 abstained alcoholics. From these, parameters of beat-to-beat heart rate and QT variability such as approximate entropy and QT variability index (QTvi) were calculated. Measures were correlated with the severity of withdrawal symptoms and with serum electrolyte concentrations. Heart rate and QTvi were significantly increased in acute alcohol withdrawal. Abstained alcoholics did not significantly differ from controls. While QTvi correlated with the severity of alcohol withdrawal symptoms, the mean QT interval duration showed an inverse relationship with serum potassium concentrations. Our data indicate increased QT variability and thus increased repolarization lability in acute alcohol withdrawal. This might add to the elevated risk for serious cardiac arrhythmias. In part, these changes might be related to increased cardiac sympathetic activity or low potassium, thus suggesting the latter as possible targets for adjuvant pharmacological therapy during withdrawal.

Perinatal risk factors and social withdrawal behaviour.

PubMed

Guedeney, Antoine; Marchand-Martin, Laetitia; Cote, Sylvana J; Larroque, Béatrice

2012-04-01

The objectives of the study were (1) to assess prevalence of social withdrawal behaviour in infants aged 12 months included in the French Perinatal Risk Factor Study Eden; (2) To study the correlation between relational withdrawal and several perinatal and parental factors assessed in the EDEN study. A longitudinal study using the ADBB scale was conducted within the Eden Cohort in the year 2008. 1,586 infants were included in the study. Fourteen percent of the children who had an ADBB assessment had a score at 5 and over on the ADBB, a scale designed to assess social withdrawal behaviour at age 0-24 months. Social withdrawal at 12 months was associated with low birth weight, low gestational age and with intra uterine growth retardation. Social withdrawal was independently associated with several maternal and paternal risk factors. The level of social withdrawal behaviour increased with a score of maternal difficulties. This study on a large longitudinally followed volunteer sample demonstrate a clear association of social withdrawal behaviour at age one with low birth weight and preterm birth, possibly mediated by parental vulnerabilities. Social withdrawal behaviour seems to be an important alarm signal to detect early on particularly in premature and small for date babies. © Springer-Verlag 2012

Simulated effects of groundwater withdrawals from aquifers in Ocean County and vicinity, New Jersey

USGS Publications Warehouse

Cauller, Stephen J.; Voronin, Lois M.; Chepiga, Mary M.

2016-10-21

Rapid population growth since the 1930s in Ocean County and vicinity, New Jersey, has placed increasing demands upon the area’s freshwater resources. To examine effects of groundwater withdrawals, a three-dimensional groundwater-flow model was developed to simulate the groundwater-flow systems of five area aquifers: the unconfined Kirkwood-Cohansey aquifer system and Vincentown aquifer, and three confined aquifers— the Rio Grande water-bearing zone, the Atlantic City 800-foot sand, and the Piney Point aquifer. The influence of withdrawals is evaluated by using transient groundwater-flow model simulations that incorporate three withdrawal schemes. These are (1) no-withdrawal conditions; (2) 2000–03 withdrawal conditions, using reported monthly withdrawals at all production wells from January 2000 through December 2003; and (3) maximum-allocation withdrawal conditions using the maximum withdrawal allowed by New Jersey Department of Environmental Protection permits at each well. Particle tracking analysis, using results from model simulations, delineated particle flow paths from production wells to the point of recharge, and estimated particle travel times.Compared with no-withdrawal conditions, 2000–03 withdrawal conditions reduced the amount of groundwater flow out of the Kirkwood-Cohansey aquifer system into streams, increased the net flow of water into other layers, reduced net flow into or out of storage, and reduced flow from the Kirkwood-Cohansey aquifer system to constant head cells.Freshwater discharging to the Barnegat Bay-Little Egg Harbor estuary from streams and groundwater is essential to maintaining the ecology of the bay. Examination of selected stress periods indicates that simulated base flow in streams flowing into the Barnegat Bay-Little Egg Harbor estuary is reduced by as much as 49 cubic feet per second for 2000 to 2003 withdrawal conditions when compared with no-withdrawal conditions.In the three confined aquifers, water levels during periods of low recharge and high withdrawals, and high recharge and low withdrawals, were examined to determine seasonal effects on the confined flow systems. The simulated potentiometric surface of the Rio Grande water-bearing zone and the Atlantic City 800-foot sand during selected stress periods indicates substantial declines from no-withdrawal conditions to 2000–03 conditions as a result of groundwater withdrawals. Cones of depression in Toms River Township, Seaside Heights and Seaside Park Boroughs, and Barnegat Light Borough developed in the potentiometric surface of the Piney Point aquifer in response to withdrawals.Maximum-allocation withdrawals decreased flow out of the Kirkwood-Cohansey aquifer system to constant head cells, increased flow out of the aquifer system to adjacent and lower layers, and reduced groundwater discharge to streams when compared with 2000–03 withdrawal conditions. Increases in withdrawals from the Rio Grande water-bearing zone, the Atlantic City 800-foot sand, and the Piney Point aquifer result in an increase in simulated net groundwater flow into these aquifers. Base-flow reduction from 2000–03 conditions to maximum-allocation conditions of 25 to 29 cubic feet per second in all streams draining to the Barnegat Bay-Little Egg Harbor also is indicated. Potentiometric surfaces of the Rio Grande water-bearing zone, Atlantic City 800-foot sand, and the Piney Point aquifer during two stress periods of simulated maximum-allocation withdrawal conditions indicated the expansion of several cones of depression developed during 2000–03 withdrawals.Simulation of average 2000–03 withdrawal conditions indicated the extent to which the groundwater-flow system is susceptible to potential saltwater intrusion into near-shore wells. Travel time from recharge to discharge location ranged from 11 to approximately 50,700 years in near-shore Kirkwood-Cohansey aquifer system wells. Those in Seaside Heights Borough, in Island Beach State Park (Berkeley Township), and in Ship Bottom Borough have particle travel times from 140 to 12,000 years and flow paths that originated under Barnegat Bay or the Atlantic Ocean from the simulation of average maximum-allocation withdrawal conditions.Travel time along flow paths to wells screened in the Rio Grande water-bearing zone and the Atlantic City 800-foot sand from recharge to discharge point ranged from nearly 530 years to greater than 3.73 million years from the simulation of average 2000–03 withdrawal conditions. Particle tracking indicated that most wells screened in these aquifers derived a large part of their recharge from the Oswego River Basin, with a small portion of flow originating either beneath Barnegat Bay or to the east beneath the Atlantic Ocean. Travel time along flow paths that start beneath either Barnegat Bay or the Atlantic Ocean ranged from 2,300 to approximately 134,000 years from the simulation of average maximum-allocation withdrawal conditions."

29 CFR 1626.13 - Withdrawal of charge.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 29 Labor 4 2012-07-01 2012-07-01 false Withdrawal of charge. 1626.13 Section 1626.13 Labor Regulations Relating to Labor (Continued) EQUAL EMPLOYMENT OPPORTUNITY COMMISSION PROCEDURES-AGE DISCRIMINATION IN EMPLOYMENT ACT § 1626.13 Withdrawal of charge. Charging parties may request withdrawal of a...

29 CFR 1626.13 - Withdrawal of charge.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 4 2010-07-01 2010-07-01 false Withdrawal of charge. 1626.13 Section 1626.13 Labor Regulations Relating to Labor (Continued) EQUAL EMPLOYMENT OPPORTUNITY COMMISSION PROCEDURES-AGE DISCRIMINATION IN EMPLOYMENT ACT § 1626.13 Withdrawal of charge. Charging parties may request withdrawal of a...

29 CFR 1626.13 - Withdrawal of charge.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 29 Labor 4 2013-07-01 2013-07-01 false Withdrawal of charge. 1626.13 Section 1626.13 Labor Regulations Relating to Labor (Continued) EQUAL EMPLOYMENT OPPORTUNITY COMMISSION PROCEDURES-AGE DISCRIMINATION IN EMPLOYMENT ACT § 1626.13 Withdrawal of charge. Charging parties may request withdrawal of a...

29 CFR 1626.13 - Withdrawal of charge.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 29 Labor 4 2014-07-01 2014-07-01 false Withdrawal of charge. 1626.13 Section 1626.13 Labor Regulations Relating to Labor (Continued) EQUAL EMPLOYMENT OPPORTUNITY COMMISSION PROCEDURES-AGE DISCRIMINATION IN EMPLOYMENT ACT § 1626.13 Withdrawal of charge. Charging parties may request withdrawal of a...

29 CFR 1626.13 - Withdrawal of charge.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 4 2011-07-01 2011-07-01 false Withdrawal of charge. 1626.13 Section 1626.13 Labor Regulations Relating to Labor (Continued) EQUAL EMPLOYMENT OPPORTUNITY COMMISSION PROCEDURES-AGE DISCRIMINATION IN EMPLOYMENT ACT § 1626.13 Withdrawal of charge. Charging parties may request withdrawal of a...

Factors Associated with Student Withdrawal from Community College

ERIC Educational Resources Information Center

Scoggin, Donna; Styron, Ronald

2006-01-01

Research was designed to identify commonalities of personal, enrollment, withdrawal, and evaluative factors as they relate to student withdrawal from community college. The study sought to identify interrelationships between identified reasons for student withdrawal and the variables of gender, race, classification status, degree sought, plans for…

20 CFR 416.355 - Withdrawal of an application.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 20 Employees' Benefits 2 2010-04-01 2010-04-01 false Withdrawal of an application. 416.355 Section 416.355 Employees' Benefits SOCIAL SECURITY ADMINISTRATION SUPPLEMENTAL SECURITY INCOME FOR THE AGED, BLIND, AND DISABLED Filing of Applications Withdrawal of Application § 416.355 Withdrawal of an...

20 CFR 404.640 - Withdrawal of an application.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 20 Employees' Benefits 2 2010-04-01 2010-04-01 false Withdrawal of an application. 404.640 Section 404.640 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL OLD-AGE, SURVIVORS AND DISABILITY INSURANCE (1950- ) Filing of Applications and Other Forms Withdrawal of Application § 404.640 Withdrawal of...

Estimated freshwater withdrawals in Texas, 1990

USGS Publications Warehouse

Lurry, Dee L.

1994-01-01

This report presents 1990 freshwater withdrawal estimates for Texas by source and category. Withdrawal source is either ground water or surface water. Withdrawal categories include: self-supplied irrigation, thermoelectric-power generation, water supply, industrial and mining, and other (domestic, commercial, livestock). Withdrawal data are aggregated by county, major aquifer, and principal river basin. Only the four major categories of irrigation, thermoelectric-power generation, water supply, and industrial and mining are illustrated in this report, although all data are tabulated.

Evaluation of effects of groundwater withdrawals at the proposed Allen combined-cycle combustion turbine plant, Shelby County, Tennessee

USGS Publications Warehouse

Haugh, Connor J.

2016-08-10

The Mississippi Embayment Regional Aquifer Study groundwater-flow model was used to simulate the potential effects of future groundwater withdrawals at the proposed Allen combined-cycle combustion turbine plant in Shelby County, Tennessee. The scenario used in the simulation consisted of a 30-year average withdrawal period followed by a 30-day maximum withdrawal period. Effects of withdrawals at the Allen plant site on the Mississippi embayment aquifer system were evaluated by comparing the difference in simulated water levels in the aquifers at the end of the 30-year average withdrawal period and at the end of the scenario to a base case without the Allen combined-cycle combustion turbine plant withdrawals. Simulated potentiometric surface declines in the Memphis aquifer at the Allen plant site were about 7 feet at the end of the 30-year average withdrawal period and 11 feet at the end of the scenario. The affected area of the Memphis aquifer at the Allen plant site as delineated by the 4-foot potentiometric surface-decline contour was 2,590 acres at the end of the 30-year average withdrawal period and 11,380 acres at the end of the scenario. Simulated declines in the underlying Fort Pillow aquifer and overlying shallow aquifer were both less than 1 foot at the end of the 30-year average withdrawal period and the end of the scenario.

Nicotinic Mechanisms Modulate Ethanol Withdrawal and Modify Time Course and Symptoms Severity of Simultaneous Withdrawal from Alcohol and Nicotine.

PubMed

Perez, Erika; Quijano-Cardé, Natalia; De Biasi, Mariella

2015-09-01

Alcohol and nicotine are among the top causes of preventable death in the United States. Unfortunately, people who are dependent on alcohol are more likely to smoke than individuals in the general population. Similarly, smokers are more likely to abuse alcohol. Alcohol and nicotine codependence affects health in many ways and leads to poorer treatment outcomes in subjects who want to quit. This study examined the interaction of alcohol and nicotine during withdrawal and compared abstinence symptoms during withdrawal from one of the two drugs only vs both. Our results indicate that simultaneous withdrawal from alcohol and nicotine produces physical symptoms that are more severe and last longer than those experienced during withdrawal from one of the two drugs alone. In animals experiencing withdrawal after chronic ethanol treatment, acute nicotine exposure was sufficient to prevent abstinence symptoms. Similarly, symptoms were prevented when alcohol was injected acutely in mice undergoing nicotine withdrawal. These experiments provide evidence for the involvement of the nicotinic cholinergic system in alcohol withdrawal. Furthermore, the outcomes of intracranial microinfusions of mecamylamine, a nonselective nicotinic receptor antagonist, highlight a major role for the nicotinic receptors expressed in medial habenula and interpeduncular nucleus during withdrawal. Overall, the data support the notion that modulating the nicotinic cholinergic system might help to maintain long-term abstinence from alcohol.

Ground-water withdrawals from the Coastal Plain of New Jersey, 1956-1980

USGS Publications Warehouse

Vowinkel, E.F.

1984-01-01

Withdrawals and site data for wells with a pump capacity of 100 ,000 gallons per day or greater in the Coastal Plain of New Jersey are stored in computer files for 1956-80. The data are aggregated by computer into tables, graphs and maps to show the distribution of ground-water withdrawals. Withdrawals are reported by type of use and aquifer for each county in the Coastal Plain. Public-supply wells withdraw the largest quantity of ground water in the Coastal Plain, followed by industrial and agricultural wells. In 1980 public-supply withdrawals were about 280 million gallons per day; the maximum monthly rate was about 355 million gallons per day in July, and the lowest was about 215 million gallons per day in February. Average industrial withdrawals were about 65 million gallons per day. Ground-water withdrawals used for agriculture vary significantly during the year. In 1980, about 75 percent of the agricultural withdrawals occurred from June through September. Several aquifers are used as sources of water supply in the Coastal Plain. Five regional aquifers are the major sources of water for public-supply, industrial, or agricultural use. In decreasing order of withdrawals in 1980, in million gallons per day, they are: The Potomac-Raritan-Magothy aquifer system, 243; Kirkwood-Cohansey aquifer system, 70; Atlantic City 800-foot sand, 21; Englishtown aquifer, 12; and the Wenonah-Mount Laurel aquifer system, 5. (USGS)

Sex differences in cannabis withdrawal symptoms among treatment-seeking cannabis users

PubMed Central

Herrmann, Evan S.; Weerts, Elise M.; Vandrey, Ryan

2015-01-01

Over 300,000 individuals enter treatment for cannabis use disorders (CUDs) in the U.S. annually. Cannabis withdrawal is associated with poor CUD treatment outcomes, but no prior studies have examined sex differences in withdrawal among treatment-seeking cannabis users. Treatment-seeking cannabis users (45 women and 91 men) completed a Marijuana Withdrawal Checklist (MWC) at treatment intake to retrospectively characterize withdrawal symptoms experienced during their most recent quit attempt. Composite Withdrawal Discomfort Scale (WDS) scores were calculated using the 14 items on the MWC that correspond to valid cannabis withdrawal symptoms described in DSM-5. Demographic and substance use characteristics, overall WDS scores, and scores on individual WDS symptoms were compared between women and men. Women had higher overall WDS scores than men, and women had higher scores than men on six individual symptoms in two domains, mood symptoms (irritability, restlessness, increased anger, violent outbursts) and gastrointestinal symptoms (nausea, stomach pain). Follow-up analyses isolating the incidence and severity of WDS symptoms demonstrated that women generally reported a higher number of individual withdrawal symptoms than men, and that they reported experiencing some symptoms as more severe. This is the first report to demonstrate that women seeking treatment for CUDs may experience more withdrawal then men during quit attempts. Prospective studies of sex differences in cannabis withdrawal are warranted. PMID:26461168

Estimated withdrawals from principal aquifers in the United States, 2000

USGS Publications Warehouse

Maupin, Molly A.; Barber, Nancy L.

2005-01-01

Fresh ground-water withdrawals from 66 principal aquifers in the United States were estimated for irrigation, public-supply, and self-supplied industrial water uses for the year 2000. Total ground-water withdrawals were 76,500 million gallons per day, or 85,800 thousand acre-feet per year for these three uses. Irrigation used the largest amount of ground water, 56,900 million gallons per day, followed by public supply with 16,000 million gallons per day, and self-supplied industrial with 3,570 million gallons per day. These three water uses represented 92 percent of the fresh groundwater withdrawals for all uses in the United States, the remaining 8 percent included self-supplied domestic, aquaculture, livestock, mining, and thermoelectric power uses. Aquifer withdrawals were categorized by five lithologic groups: unconsolidated and semiconsolidated sand and gravel aquifers, carbonate-rock aquifers, igneous and metamorphic-rock aquifers, sandstone aquifers, and sandstone and carbonate-rock aquifers. Withdrawals from aquifers that were not included in one of the 66 principal aquifers were reported in an “Other” aquifers group. The largest withdrawals in the United States were from unconsolidated and semiconsolidated sand and gravel aquifers, which accounted for 80 percent of total withdrawals from all aquifers. Carbonate-rock aquifers provided 8 percent of the withdrawals, and igneous and metamorphic-rock aquifers, 6 percent. Withdrawals from sandstone aquifers, from sandstone and carbonate-rock aquifers, and from the “Other” aquifers category each constituted about 2 percent of the total withdrawals reported.Fifty-five percent of the total withdrawals for irrigation, public-supply, and self-supplied industrial water uses were provided by the High Plains aquifer, California Central Valley aquifer system, the Mississippi River Valley alluvial aquifer, and the Basin and Range basin-fill aquifers. These aquifers provided most of the withdrawals for irrigation. The High Plains aquifer was the most intensively used aquifer in the United States. This aquifer provided 23 percent of the total withdrawals from all aquifers for irrigation, public-supply, and self-supplied industrial water uses combined, and 30 percent of the total withdrawals from all aquifers for irrigation. The primary aquifers used for public supply were the glacial sand and gravel aquifers of the Northeastern and North-Central States, the California Coastal Basin aquifers, the Floridan aquifer system, the Basin and Range basin-fill aquifers, and the Coastal lowlands aquifer system along the Gulf Coast. These five aquifers provided 43 percent of the total withdrawals from all aquifers for public supply. The glacial sand and gravel aquifers, Coastal lowlands aquifer system, Floridan aquifer system, and Cambrian-Ordovician aquifer system were the primary sources of water for self-supplied industrial use; these aquifers provided 46 percent of the total ground-water withdrawals for that use.

Youth Withdrawal Moderates the Relationhips between Neighborhood Factors and Internalizing Symptoms in Adolescence

PubMed Central

Rabinowitz, Jill A.; Drabick, Deborah A.G.; Reynolds, Maureen D.

2015-01-01

Adolescents higher in temperamental withdrawal are at risk for anxiety and depressive symptoms; however, not all youth higher in withdrawal exhibit internalizing symptoms, suggesting that contextual factors may influence these relationships. We examined whether youth withdrawal moderates the relationships between neighborhood processes (crime, social cohesion) and internalizing symptoms and whether findings were consistent with diathesis-stress or differential susceptibility hypotheses. Participants were 775 adolescents (M=15.50 ± 0.56 years, 72% male, 76% White). Adolescents higher in withdrawal manifested higher internalizing symptoms in the context of lower neighborhood crime and lower neighborhood social cohesion than youth lower in withdrawal, supporting diathesis-stress. These findings elucidate neighborhood processes associated with internalizing symptoms, which can inform models of risk and resilience for these symptoms among children who differ in temperamental withdrawal. PMID:26149949

Ground-Water Availability in the Wailuku Area, Maui, Hawai'i

USGS Publications Warehouse

Gingerich, Stephen B.

2008-01-01

Most of the public water supply in Maui, Hawai'i, is from a freshwater lens in the Wailuku area of the island. Because of population growth, ground-water withdrawals from wells in this area increased from less than 10 Mgal/d during 1970 to about 23 Mgal/d during 2006. In response to increased withdrawals from the freshwater lens in the Wailuku area, water levels declined, the transition zone between freshwater and saltwater became shallower, and the chloride concentrations of water pumped from wells increased. These responses led to concern over the long-term sustainability of withdrawals from existing and proposed wells. A three-dimensional numerical ground-water flow and transport model was developed to simulate the effects of selected withdrawal and recharge scenarios on water levels, on the transition zone between freshwater and saltwater, and on surface-water/ground-water interactions. The model was constructed using time-varying recharge, withdrawals, and ocean levels. Hydraulic characteristics used to construct the model were initially based on published estimates but ultimately were varied to obtain better agreement between simulated and measured water levels and salinity profiles in the modeled area during the period 1926-2006. Scenarios included ground-water withdrawal at 2006 and 1996 rates and locations with average recharge (based on 2000-04 land use and 1926-2004 rainfall) and withdrawal at redistributed rates and locations with several different recharge scenarios. Simulation results indicate that continuing 1996 and 2006 withdrawal distributions into the future results in decreased water levels, a thinner freshwater lens, increased salinity from pumped wells, and higher salinity at several current withdrawal sites. A redistributed withdrawal condition in which ground-water withdrawal was redistributed to maximize withdrawal and minimize salinities in the withdrawn water was determined. The redistributed withdrawal simulates 27.1 Mgal/d of withdrawal from 14 wells or well fields in the Wailuku area. Simulation results from the five scenarios that include redistributed withdrawal conditions indicate the following for the Wailuku Aquifer Sector: (1) withdrawal during times of average recharge rates cause average water levels to decrease 2-3 ft and the transition zone to become more than 200 ft shallower after 150 years; (2) a 5-yr drought condition similar to the 1998-2002 drought results in additional salinity increases after 30 years (12.5 years of normal recharge after drought conditions) but only one well has salinity increases of concern; (3) additional recharge from restored streamflow significantly increases water levels, thickens the freshwater body, and decreases salinity at withdrawal sites in the Waihe'e and 'Iao Aquifer Systems; and (4) a complete removal of irrigation recharge decreases water levels and increases salinity in the central isthmus where irrigation is reduced, but recharge through restored streams still significantly increases water levels, thickens the freshwater body, and decreases salinity at withdrawal sites in the Waihe'e and 'Iao Aquifer Systems.

Suppression of hypothalamic-pituitary-adrenal axis by acute heroin challenge in rats during acute and chronic withdrawal from chronic heroin administration

PubMed Central

Zhou, Yan; Leri, Francesco; Ho, Ann; Kreek, Mary Jeanne

2013-01-01

It is known that heroin dependence and withdrawal are associated with changes in the hypothalamic-pituitary-adrenal (HPA) axis. The objective of these studies in rats was to systematically investigate the level of HPA activity and response to a heroin challenge at two time points during heroin withdrawal, and to characterize the expression of associated stress-related genes 30 minutes after each heroin challenge. Rats received chronic (10-day) intermittent escalating-dose heroin administration (3×2.5 mg/kg/day on day 1; 3×20 mg/kg/day by day 10). Hormonal and neurochemical assessments were performed in acute (12 hours after last heroin injection) and chronic (10 days after the last injection) withdrawal. Both plasma ACTH and corticosterone levels were elevated during acute withdrawal, and heroin challenge at 20 mg/kg (the last dose of chronic escalation) at this time point attenuated this HPA hyperactivity. During chronic withdrawal, HPA hormonal levels returned to baseline, but heroin challenge at 5 mg/kg decreased ACTH levels. In contrast, this dose of heroin challenge stimulated the HPA axis in heroin naïve rats. In the anterior pituitary, pro-opiomelanocortin (POMC) mRNA levels were increased during acute withdrawal and retuned to control levels after chronic withdrawal. In the medial hypothalamus, however, the POMC mRNA levels were decreased during acute withdrawal, and increased after chronic withdrawal. Our results suggest a long-lasting change in HPA abnormal responsivity during chronic heroin withdrawal. PMID:23771528

Sex differences in cannabis withdrawal symptoms among treatment-seeking cannabis users.

PubMed

Herrmann, Evan S; Weerts, Elise M; Vandrey, Ryan

2015-12-01

Over 300,000 individuals enter treatment for cannabis-use disorders (CUDs) in the United States annually. Cannabis withdrawal is associated with poor CUD-treatment outcomes, but no prior studies have examined sex differences in withdrawal among treatment-seeking cannabis users. Treatment-seeking cannabis users (45 women and 91 men) completed a Marijuana Withdrawal Checklist (Budney, Novy, & Hughes, 1999, Budney, Moore, Vandrey, & Hughes, 2003) at treatment intake to retrospectively characterize withdrawal symptoms experienced during their most recent quit attempt. Scores from the 14-item Composite Withdrawal Discomfort Scale (WDS), a subset of the Marijuana Withdrawal Checklist that corresponds to valid cannabis withdrawal symptoms described in the Diagnostic and Statistical Manual of Mental Disorders (5th ed.; APA, 2013) were calculated. Demographic and substance-use characteristics, overall WDS scores, and scores on individual WDS symptoms were compared between women and men. Women had higher overall WDS scores than men, and women had higher scores than men on 6 individual symptoms in 2 domains, mood symptoms (i.e., irritability, restlessness, increased anger, violent outbursts), and gastrointestinal symptoms (i.e., nausea, stomach pain). Follow-up analyses isolating the incidence and severity of WDS symptoms demonstrated that women generally reported a higher number of individual withdrawal symptoms than men, and that they reported experiencing some symptoms as more severe. This is the first report to demonstrate that women seeking treatment for CUDs may experience more withdrawal then men during quit attempts. Prospective studies of sex differences in cannabis withdrawal are warranted. (PsycINFO Database Record (c) 2015 APA, all rights reserved).

Predictors of 12-Months Relapse After Withdrawal Treatment in Hospitalized Patients With Chronic Migraine Associated With Medication Overuse: A Longitudinal Observational Study.

PubMed

Raggi, Alberto; Giovannetti, Ambra M; Leonardi, Matilde; Sansone, Emanuela; Schiavolin, Silvia; Curone, Marcella; Grazzi, Licia; Usai, Susanna; D'Amico, Domenico

2017-01-01

Studies addressing relapse rates conflate relapse into chronic migraine (CM) and medication overuse (MO), and the consequent need to repeat withdrawal. We aim to identify 12-months predictors of relapse into CM (based on headaches frequency) separately from occurrence of another structured withdrawal. Hospitalized patients with CM-MO under withdrawal were enrolled. Candidate predictors included demographic, disability, quality of life, depression scores, general self-efficacy, social support, headaches frequency and intensity, class of overused medications, history of withdrawal treatment in the three years prior to enrollment, attendance to emergency room (ER) between enrollment and follow-up, nonattendance to outpatient neurological examinations. Logistic regressions was used to address the significant predictors for the two outcomes. Complete data were available for 177 patients: 60 (33.9%) relapsed into CM, 38 (21.5%) underwent another withdrawal treatment. Recent history of withdrawal treatments, ER admission after discharge and high baseline BDI-II scores were significant predictors in both models. In addition to this, high baseline headache frequency predicted relapse into another withdrawal treatment. Predictors or relapse into CM and of occurrence of another withdrawal by 12-months are somehow similar. It is important to assess presence of recent previous withdrawal treatments and to plan regular follow-up afterwards, in particular for patients with high headache frequency and relevant mood disturbances: in this way, it will be more likely that situations requiring further structured withdrawal treatments can be identified before patients have to refer to ER. © 2016 American Headache Society.

17 CFR 9.8 - Practice before the Commission.

Code of Federal Regulations, 2013 CFR

2013-04-01

... of enabling the party to obtain other counsel or representative. (c) Withdrawal of representation. Withdrawal from representation of a party will be only by leave of the Commission. Such leave to withdraw may... party represented has actual knowledge of the withdrawal, and such affidavit must include the name and...

17 CFR 171.13 - Practice before the Commission.

Code of Federal Regulations, 2014 CFR

2014-04-01

... enabling the party to obtain other counsel or representative. (c) Withdrawal from representation. Withdrawal from representation of a party will be only by leave of the Commission. Such leave to withdraw may... actual knowledge of the withdrawal and providing the name and address of a successor counsel (or...

17 CFR 9.8 - Practice before the Commission.

Code of Federal Regulations, 2011 CFR

2011-04-01

... of enabling the party to obtain other counsel or representative. (c) Withdrawal of representation. Withdrawal from representation of a party will be only by leave of the Commission. Such leave to withdraw may... party represented has actual knowledge of the withdrawal, and such affidavit must include the name and...

17 CFR 9.8 - Practice before the Commission.

Code of Federal Regulations, 2014 CFR

2014-04-01

... of enabling the party to obtain other counsel or representative. (c) Withdrawal of representation. Withdrawal from representation of a party will be only by leave of the Commission. Such leave to withdraw may... party represented has actual knowledge of the withdrawal, and such affidavit must include the name and...

17 CFR 9.8 - Practice before the Commission.

Code of Federal Regulations, 2010 CFR

2010-04-01

... of enabling the party to obtain other counsel or representative. (c) Withdrawal of representation. Withdrawal from representation of a party will be only by leave of the Commission. Such leave to withdraw may... party represented has actual knowledge of the withdrawal, and such affidavit must include the name and...

17 CFR 9.8 - Practice before the Commission.

Code of Federal Regulations, 2012 CFR

2012-04-01

... of enabling the party to obtain other counsel or representative. (c) Withdrawal of representation. Withdrawal from representation of a party will be only by leave of the Commission. Such leave to withdraw may... party represented has actual knowledge of the withdrawal, and such affidavit must include the name and...

40 CFR 97.86 - Withdrawal from NOX Budget Trading Program.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Withdrawal from NOX Budget Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Individual Unit Opt-ins. § 97.86 Withdrawal from NOX Budget Trading Program. (a) Requesting withdrawal. To...

43 CFR 3732.1 - Act ineffective as to other withdrawals.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Act ineffective as to other withdrawals... LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) PUBLIC LAW 359; MINING IN POWERSITE WITHDRAWALS: GENERAL Withdrawals Other Than for Powersite Purposes § 3732.1 Act ineffective as to...

Withdrawal When You’re Pregnant

Cancer.gov

The nicotine in cigarettes is addictive. That’s why many smokers who decide to quit go through some degree of withdrawal. Quitting smoking while you’re pregnant won’t change withdrawal symptoms. You may still be uncomfortable or feel not quite like yourself. But withdrawal from cigarettes will not harm your baby.

19 CFR 144.36 - Withdrawal for transportation.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 19 Customs Duties 2 2010-04-01 2010-04-01 false Withdrawal for transportation. 144.36 Section 144... § 144.36 Withdrawal for transportation. (a) Time limit. Merchandise may be withdrawn from warehouse for transportation to another port of entry if withdrawal for consumption or exportation can be accomplished at the...

19 CFR 144.36 - Withdrawal for transportation.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 19 Customs Duties 2 2013-04-01 2013-04-01 false Withdrawal for transportation. 144.36 Section 144... § 144.36 Withdrawal for transportation. (a) Time limit. Merchandise may be withdrawn from warehouse for transportation to another port of entry if withdrawal for consumption or exportation can be accomplished at the...

19 CFR 144.36 - Withdrawal for transportation.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 19 Customs Duties 2 2011-04-01 2011-04-01 false Withdrawal for transportation. 144.36 Section 144... § 144.36 Withdrawal for transportation. (a) Time limit. Merchandise may be withdrawn from warehouse for transportation to another port of entry if withdrawal for consumption or exportation can be accomplished at the...

19 CFR 144.36 - Withdrawal for transportation.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 19 Customs Duties 2 2012-04-01 2012-04-01 false Withdrawal for transportation. 144.36 Section 144... § 144.36 Withdrawal for transportation. (a) Time limit. Merchandise may be withdrawn from warehouse for transportation to another port of entry if withdrawal for consumption or exportation can be accomplished at the...

19 CFR 144.38 - Withdrawal for consumption.

Code of Federal Regulations, 2010 CFR

2010-04-01

... provided in § 141.61(e) of this chapter. (b) Withdrawal for exportation to Canada or Mexico. A withdrawal... withdrawal of cigars, cigarettes, or cigarette papers or tubes subject to internal revenue tax, the statement... will be finally due upon liquidation. (e) Permit for release of merchandise. When the duties and other...

5 CFR 1650.31 - Age-based withdrawals.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 5 Administrative Personnel 3 2012-01-01 2012-01-01 false Age-based withdrawals. 1650.31 Section... FUNDS FROM THE THRIFT SAVINGS PLAN In-Service Withdrawals § 1650.31 Age-based withdrawals. (a) A participant who has reached age 591/2 and who has not separated from Government employment is eligible to...

5 CFR 1650.31 - Age-based withdrawals.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 5 Administrative Personnel 3 2010-01-01 2010-01-01 false Age-based withdrawals. 1650.31 Section... FUNDS FROM THE THRIFT SAVINGS PLAN In-Service Withdrawals § 1650.31 Age-based withdrawals. (a) A participant who has reached age 591/2 and who has not separated from Government employment is eligible to...

5 CFR 1650.31 - Age-based withdrawals.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 5 Administrative Personnel 3 2013-01-01 2013-01-01 false Age-based withdrawals. 1650.31 Section... FUNDS FROM THE THRIFT SAVINGS PLAN In-Service Withdrawals § 1650.31 Age-based withdrawals. (a) A participant who has reached age 591/2 and who has not separated from Government service is eligible to...

5 CFR 1650.31 - Age-based withdrawals.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 5 Administrative Personnel 3 2014-01-01 2014-01-01 false Age-based withdrawals. 1650.31 Section... FUNDS FROM THE THRIFT SAVINGS PLAN In-Service Withdrawals § 1650.31 Age-based withdrawals. (a) A participant who has reached age 591/2 and who has not separated from Government service is eligible to...

5 CFR 1650.31 - Age-based withdrawals.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 5 Administrative Personnel 3 2011-01-01 2011-01-01 false Age-based withdrawals. 1650.31 Section... FUNDS FROM THE THRIFT SAVINGS PLAN In-Service Withdrawals § 1650.31 Age-based withdrawals. (a) A participant who has reached age 591/2 and who has not separated from Government employment is eligible to...

40 CFR 97.86 - Withdrawal from NOX Budget Trading Program.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Withdrawal from NOX Budget Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Individual Unit Opt-ins. § 97.86 Withdrawal from NOX Budget Trading Program. (a) Requesting withdrawal. To...

20 CFR 408.355 - Can you withdraw your application?

Code of Federal Regulations, 2011 CFR

2011-04-01

... 20 Employees' Benefits 2 2011-04-01 2011-04-01 false Can you withdraw your application? 408.355 Section 408.355 Employees' Benefits SOCIAL SECURITY ADMINISTRATION SPECIAL BENEFITS FOR CERTAIN WORLD WAR II VETERANS Filing Applications Withdrawal of Application § 408.355 Can you withdraw your application...

19 CFR 144.38 - Withdrawal for consumption.

Code of Federal Regulations, 2014 CFR

2014-04-01

... provided in § 141.61(e) of this chapter. (b) Withdrawal for exportation to Canada or Mexico. A withdrawal... withdrawal of cigars, cigarettes, or cigarette papers or tubes subject to internal revenue tax, the statement... will be finally due upon liquidation. (e) Permit for release of merchandise. When the duties and other...

19 CFR 144.38 - Withdrawal for consumption.

Code of Federal Regulations, 2011 CFR

2011-04-01

... provided in § 141.61(e) of this chapter. (b) Withdrawal for exportation to Canada or Mexico. A withdrawal... withdrawal of cigars, cigarettes, or cigarette papers or tubes subject to internal revenue tax, the statement... will be finally due upon liquidation. (e) Permit for release of merchandise. When the duties and other...

19 CFR 144.38 - Withdrawal for consumption.

Code of Federal Regulations, 2013 CFR

2013-04-01

... provided in § 141.61(e) of this chapter. (b) Withdrawal for exportation to Canada or Mexico. A withdrawal... withdrawal of cigars, cigarettes, or cigarette papers or tubes subject to internal revenue tax, the statement... will be finally due upon liquidation. (e) Permit for release of merchandise. When the duties and other...

19 CFR 144.38 - Withdrawal for consumption.

Code of Federal Regulations, 2012 CFR

2012-04-01

... provided in § 141.61(e) of this chapter. (b) Withdrawal for exportation to Canada or Mexico. A withdrawal... withdrawal of cigars, cigarettes, or cigarette papers or tubes subject to internal revenue tax, the statement... will be finally due upon liquidation. (e) Permit for release of merchandise. When the duties and other...

47 CFR 1.8 - Withdrawal of papers.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 47 Telecommunication 1 2011-10-01 2011-10-01 false Withdrawal of papers. 1.8 Section 1.8 Telecommunication FEDERAL COMMUNICATIONS COMMISSION GENERAL PRACTICE AND PROCEDURE General Rules of Practice and Procedure General § 1.8 Withdrawal of papers. The granting of a request to dismiss or withdraw an...

47 CFR 1.8 - Withdrawal of papers.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 47 Telecommunication 1 2010-10-01 2010-10-01 false Withdrawal of papers. 1.8 Section 1.8 Telecommunication FEDERAL COMMUNICATIONS COMMISSION GENERAL PRACTICE AND PROCEDURE General Rules of Practice and Procedure General § 1.8 Withdrawal of papers. The granting of a request to dismiss or withdraw an...

12 CFR 925.26 - Voluntary withdrawal from membership.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 12 Banks and Banking 7 2010-01-01 2010-01-01 false Voluntary withdrawal from membership. 925.26 Section 925.26 Banks and Banking FEDERAL HOUSING FINANCE BOARD FEDERAL HOME LOAN BANK MEMBERS AND HOUSING ASSOCIATES MEMBERS OF THE BANKS Withdrawal and Removal From Membership § 925.26 Voluntary withdrawal from...

A Detection Model of College Withdrawal

ERIC Educational Resources Information Center

Pleskac, Timothy J.; Keeney, Jessica; Merritt, Stephanie M.; Schmitt, Neal; Oswald, Frederick L.

2011-01-01

Many students during their college careers consider withdrawing from their respective college or university. Understanding why some students decide to withdraw yet others persist has implications for both the well being of students as well as for institutes of higher education. The present study develops a model of the decision to withdraw drawing…

8 CFR 1244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 8 Aliens and Nationality 1 2013-01-01 2013-01-01 false Withdrawal of Temporary Protected Status... JUSTICE IMMIGRATION REGULATIONS TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 1244.14 Withdrawal of Temporary Protected Status. (a) Authority of director. The director may withdraw the status of...

8 CFR 1244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 8 Aliens and Nationality 1 2012-01-01 2012-01-01 false Withdrawal of Temporary Protected Status... JUSTICE IMMIGRATION REGULATIONS TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 1244.14 Withdrawal of Temporary Protected Status. (a) Authority of director. The director may withdraw the status of...

8 CFR 1244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 8 Aliens and Nationality 1 2010-01-01 2010-01-01 false Withdrawal of Temporary Protected Status... JUSTICE IMMIGRATION REGULATIONS TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 1244.14 Withdrawal of Temporary Protected Status. (a) Authority of director. The director may withdraw the status of...

8 CFR 244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 8 Aliens and Nationality 1 2012-01-01 2012-01-01 false Withdrawal of Temporary Protected Status... TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 244.14 Withdrawal of Temporary Protected Status. (a) Authority of USCIS. USCIS may withdraw the status of an alien granted Temporary Protected...

8 CFR 244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 8 Aliens and Nationality 1 2014-01-01 2014-01-01 false Withdrawal of Temporary Protected Status... TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 244.14 Withdrawal of Temporary Protected Status. (a) Authority of USCIS. USCIS may withdraw the status of an alien granted Temporary Protected...

8 CFR 1244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 8 Aliens and Nationality 1 2014-01-01 2014-01-01 false Withdrawal of Temporary Protected Status... JUSTICE IMMIGRATION REGULATIONS TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 1244.14 Withdrawal of Temporary Protected Status. (a) Authority of director. The director may withdraw the status of...

8 CFR 1244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 8 Aliens and Nationality 1 2011-01-01 2011-01-01 false Withdrawal of Temporary Protected Status... JUSTICE IMMIGRATION REGULATIONS TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 1244.14 Withdrawal of Temporary Protected Status. (a) Authority of director. The director may withdraw the status of...

8 CFR 244.14 - Withdrawal of Temporary Protected Status.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 8 Aliens and Nationality 1 2013-01-01 2013-01-01 false Withdrawal of Temporary Protected Status... TEMPORARY PROTECTED STATUS FOR NATIONALS OF DESIGNATED STATES § 244.14 Withdrawal of Temporary Protected Status. (a) Authority of USCIS. USCIS may withdraw the status of an alien granted Temporary Protected...

Attempting to Predict Withdrawal from Higher Education Using Demographic, Psychological and Educational Measures

ERIC Educational Resources Information Center

Charlton, John P.; Barrow, Corinne; Hornby-Atkinson, Pat

2006-01-01

Demographic, psychological and secondary level examination measures were obtained at the start of undergraduate courses in an attempt to predict first-year higher education (HE) withdrawal. As usual, withdrawal was greatest for males. Overall, intrinsic motivation and independent study expectations were better predictors of withdrawal than…

29 CFR 2520.104-49 - Alternative method of compliance for certain simplified employee pensions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... employer contributions will be made and those IRAs are subject to provisions that prohibit withdrawal of... or withdraw funds from the IRAs, including restrictions that allow rollovers or withdrawals but... purposes, (viii) The statutory provisions concerning withdrawal of funds from a SEP-IRA and the...

45 CFR 400.301 - Withdrawal from the refugee program.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 45 Public Welfare 2 2010-10-01 2010-10-01 false Withdrawal from the refugee program. 400.301... Waivers and Withdrawals § 400.301 Withdrawal from the refugee program. (a) In the event that a State... assistance, social services, preventive health, and an unaccompanied minors program if appropriate. A State...

Preparation & characterization of SiO2 interface layer by dip coating technique on carbon fibre for Cf/SiC composites

NASA Astrophysics Data System (ADS)

Kumar, Kundan; Jariwala, C.; Pillai, R.; Chauhan, N.; Raole, P. M.

2015-08-01

Carbon fibres (Cf) are one of the most important reinforced materials for ceramic matrix composites such as Cf - SiC composites and they are generally sought for high temperature applications in as space application, nuclear reactor and automobile industries. But the major problem arise when Cf reinforced composites exposed to high temperature in an oxidizing environment, Cf react with oxygen and burnt away. In present work, we have studied the effect of silica (SiO2) coating as a protective coating on Cf for the Cf / SiC composites. The silica solution prepared by the sol-gel process and coating on Cf is done by dip coating technique with varying the withdrawing speed i.e. 2, 5, 8 mm/s with fixed dipping cycle (3 Nos.). The uniform silica coating on the Cf is shown by the Scanning Electron Microscope (SEM) analysis. The tensile test shows the increase in tensile strength with respect to increase in withdrawing speed. The isothermal oxidation analysis confirmed enhancement of oxidation resistance of silica coated Cf as compared tothe uncoated Cf.

Singlet-triplet energy differences in divalent five membered cyclic conjugated Arduengo-type carbenes XC2HN2M (M = C, Si, Ge, Sn, and Pb; X = F, Cl, Br, and I)

NASA Astrophysics Data System (ADS)

Vessally, Esmail; Dehbandi, Behnam; Ahmadi, Elaheh

2016-09-01

Singlet-triplet energy differences in Arduengo-type carbenes XC2HN2C compared and contrasted with their sila, germa, stana and plumba analogues; at B3LYP/6-311++G** level of theory. Free Gibbs energy differences between triplet (t) and singlet (s) states (Δ G(t-s)) change in the following order: plumbylenes > stannylenes > germylenes > silylenes > carbenes. The singlet states in XC2HN2C are generally more stable when the electron withdrawing groups such as-F was used at β-position. However, the singlet states in XC2N2HM (M = Si, Ge, Sn, and Pb) are generally more stable when the withdrawing groups such as-F was placed. The puckering energy is investigated for each the singlet and triplet states. The DFT calculations found the linear correlation to size of the group 14 divalent element (M), the ∠N-M-N angle, and the Δ(LUMO-HOMO) of XC2HN2M.

RETRACTED: A fluorescent molecularly-imprinted polymer gate with temperature and pH as inputs for detection of alpha-fetoprotein.

PubMed

Karfa, Paramita; Roy, Ekta; Patra, Santanu; Kumar, Deepak; Madhuri, Rashmi; Sharma, Prashant K

2016-04-15

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal). This article has been retracted at the request of the Editor following concerns raised by a reader. The article reuses an electron micrograph from a previous publication while claiming that these are different particles. Fig. 1C/D were reused from Fig. 2B published in Biosensors and Bioelectronics, Volume 73, 15 November 2015, Pages 234–244, https://doi.org/10.1016/j.bios.2015.06.005. This problem with the data presented casts doubt on all the data, and accordingly also the conclusions based on that data, in this publication. As such this article represents a severe abuse of the scientific publishing system. The scientific community takes a very strong view on this matter and apologies are offered to readers of the journal that this was not detected during the submission process. Copyright © 2015 Elsevier B.V. All rights reserved.