bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spin Multiplicity Dependence of Nonlinear Optical Properties
Authors: Jha Prakash Chandra , Rinkevicius Zilvinas , Ågren Hans 
Published: February 2009

AbstractSpin‐restricted time‐dependent DFT for open‐shell systems is used to study the spin multiplicity dependence of nonlinear optical coefficients. Calculations are performed for various spin states of the pyrrole radical (see figure). The results indicate a substantial dependence on spin multiplicity of the NLO properties, which are sensitive to the basis set compared to closed shells at the DFT level of theory.magnified imageOpen‐shell spin‐restricted time‐dependent density functional theory is applied to explore the spin multiplicity dependence of linear and nonlinear optical properties. An open‐shell neutral conjugated system, the C4H4N radical in the doublet X2A2, quartet X4A2, and sextet X6A1 states, is chosen as a model system to illustrate various aspects of the theory. It is found that irrespective of the exchange‐correlation functional employed, the components of the polarizability α(−ω,ω) and first hyperpolarizability β(−2 ω,ω,ω) show very different dependency with respect to the multiplicity, with an increasing trend for higher spin states. This is rationalized by the decrease in conjugation and stability of the system with increasing multiplicity, and by the way the interaction between unpaired electrons and the external field is shielded by remaining electrons of the molecule. The study suggests the applicability of open‐shell systems for frequency‐dependent nonlinear optical properties and for the possibility of spin control for such properties.
Relationship between the Molecular Structure of Cyanine Dyes and the Vibrational Fine Structure of their Electronic Absorption Spectra
Authors: Mustroph Heinz , Reiner Knut , Mistol Jürgen , Ernst Steffen , Keil Dietmar , Hennig Lothar 
Published: February 2009

AbstractVibronic sub‐bandsin the electronic absorption spectra of symmetrical cyanine dyes (see picture) are attributed to the symmetric CC valence vibration of the polymethine chain in the excited state. The3J(H,H) coupling constants in the polymethine chain can be used to characterize the bond localization within the chain in the ground state and thus to explain the intensity distribution of the sub‐bands.magnified imageElectronic absorption spectra of symmetrical cyanine dyes show vibronic sub‐bands, attributed to the symmetric CC valence vibration of the polymethine chain in the electronic excited state. Displacements in the equilibrium configuration between electronic ground and excited states of cyanine dyes lead to longer CC bonds in the excited state. Additionally, in the electronic ground state, a small degree of bond localisation always remains in the chain depending on the different heterocyclic terminal groups. Our investigations suggest that we can use3J(H,H) coupling constants in the polymethine chain to characterise the bond localisation within the chain. Based on these values and the Franck–Condon principle, the intensity distribution among the vibrational sub‐bands can be explained.
Therapist characteristics influencing the quality of alliance in long‐term psychotherapy
Authors: Hersoug Anne Grete , Høglend Per , Havik Odd , von der Lippe Anna , Monsen Jon 
Published: February 2009

AbstractThis study explored therapist characteristics associated with the development of working alliance in long‐term therapies, up to 120 sessions. The quality of working alliance was rated by both patients (n = 201) and therapists (n = 61) at sessions 3, 12, 20 and every 20th successive session. Therapists' self‐reported scores on the ‘cold/detached’ dimension of Inventory of Interpersonal Problems‐64 tapping therapists' interpersonal style, such as being distanced, disconnected or indifferent, had a negative impact on the working alliance as rated both by patients and therapists. More professional training was associated with poorer quality of working alliance, as rated by patients. A trend indicated that more experienced therapists rated the alliance lower at all sessions. Therapists' report of better maternal care up to their adolescence had a positive impact on patients' rating of alliance. Clinical implications are discussed. Copyright © 2009 John Wiley & Sons, Ltd.
The use of the repertory grid technique to examine staff beliefs about clients with dual diagnosis
Authors: Ralley Catriona , Allott Rory , Hare Dougal Julian , Wittkowski Anja 
Published: February 2009

AbstractAim: This paper reports a study exploring how individual psychiatric staff construes clients with psychosis who misuse substances.Background: A dual diagnosis of substance misuse is common in clients with psychosis. Previous studies have suggested that psychiatric staff feel ill‐equipped to work with these clients, and hold negative views of them, affecting client care and recovery. Understanding staff attitudes can inform training and practice.Method: Twelve psychiatric nursing staff working in an inpatient service for adults with enduring mental health difficulties in England were interviewed. Using a repertory grid technique, staff were asked to describe clients and acquaintances who did and did not misuse substances, themselves and colleagues.Findings: All staff made critical judgements of some clients, particularly clients with dual diagnosis, but were less judgemental towards acquaintances who misused substances. Staff who used fewer dimensions to construe people appeared to make a clear distinction between clients and non‐clients. This distinction was not apparent for staff with more cognitively complex construct systems. Specific factors that could be implicated in the organization of individuals' construct systems included personal experience of services as a carer; these staff made less distinction between clients and non‐clients.Conclusion: Further training is needed for staff working with clients with a dual diagnosis. Training packages need to consider the personal experiences and views of staff. Reducing the boundaries between staff and clients might enable staff to better understand the actions of clients and improve client care. Copyright © 2009 John Wiley & Sons, Ltd.
The post‐traumatic embitterment disorder Self‐Rating Scale (PTED Scale)
Authors: Linden Michael , Baumann Kai , Lieberei Barbara , Rotter Max 
Published: February 2009

AbstractThe present study introduces the Post‐Traumatic Embitterment Disorder Self‐Rating Scale (PTED Scale), which asks for prolonged and disabling embitterment reactions in the aftermath of negative life events. The PTED Scale was administered to four independent samples of patients and normals. Internal consistency and test–retest reliability were high. Factor analysis indicated a two‐factor solution, accounting for 55.25% of the total variance. The PTED Scale discriminated significantly between patients who had been classified according to clinical judgement as suffering from pathological embitterment. Correlations with related instruments demonstrated good convergent validity. Data obtained from a non‐clinical sample indicated a prevalence of clinically relevant embitterment in the general population of about 2.5%. The PTED Scale is a reliable and valid measure for embitterment as an emotional reaction to a negative life event. Furthermore, results demonstrate that reactive embitterment in connection to a negative life event is a prevalent phenomenon among clinical and non‐clinical populations. Copyright © 2009 John Wiley & Sons, Ltd.
Design of high‐gain wide‐band harmonic self‐oscillating mixers
Authors: Fernández M. , Ver Hoeye S. , Herrán L. F. , Las Heras F. 
Published: February 2009

AbstractIn this work, a new design method is presented for the design of wide‐band harmonic self‐oscillating mixers (HSOM) with high conversion gain. The optimum design for the HSOM circuit is obtained using bifurcation analysis‐ and control‐techniques in combination with nonlinear optimization techniques based on the use of an auxiliary generator. The design method is illustrated through the design of an 11.25–1.5 GHz third harmonic self‐oscillating mixer (3HSOM) with a 6.5 dB down‐conversion gain over a 1.6 GHz bandwidth. It is also demonstrated how the frequency variation of the conversion gain can be shaped by means of the use of bifurcation control techniques. A good agreement between the simulated and experimental results has been found. Copyright © 2009 John Wiley & Sons, Ltd.
Allylic Amination Using Well‐Defined [(NHC)Pd(η3‐allyl)Cl] Complexes and PPh3
Authors: Roland Sylvain , Cotet William , Mangeney Pierre 
Published: February 2009

AbstractThe allylic amination reaction catalyzed by [(NHC)Pd(allyl)Cl] complexes has been studied, and the presence of PPh3 found to be essential for the catalytic system to be active.[(1‐Mesityl‐3‐methylimidazol‐2‐ylidene)Pd(η3‐C3H5)Cl] has been used to optimize the conditions of the reaction with (E)‐1,3‐diphenylprop‐3‐enyl acetate and benzylamine under biphasic conditions (aqueous base/CH2Cl2). The best yields of isolated product (98 %) were obtained using aqueous 1 M K2CO3. The influence of the NHC ligand and the allyl fragment on the pre‐catalyst was also examined. Two new neutral [(NHC)Pd(η3‐1‐RC3H4)Cl] complexes [NHC = 1‐mesityl‐3‐methylimidazol‐2‐ylidene or 1‐(2,6‐diisopropylphenyl)‐3‐methylimidazol‐2‐ylidene; R = H or Ph] have been prepared and a decrease of the reaction time observed with the former. NMR studies have shown that this pre‐catalyst is more easily activated than its η3‐allyl analogue and that the predominant activation pathway involves attack of the amine at the allyl fragment. This reaction occurs exclusively in the presence of PPh3, thus suggesting that cationic [(NHC)Pd(allyl)(PPh3)]+ complexes, which are more electrophilic, are formed in situ and allow the amine to react with the allyl fragment. A tetrafluoroborate cationic complex has therefore been prepared from [(NHC)Pd(allyl)Cl], PPh3, and AgBF4 and fully characterized. This complex is an active pre‐catalyst in the allylic amination reaction. The scope of the reaction was examined under the optimized reaction conditions with several different nitrogen nucleophiles and allylic acetates. The amination products were obtained in yields ranging from 73 to >98 %, except for that from cyclohexenyl acetate and dibenzylamine. Finally, the reaction performed directly with the allylic alcohol and benzylamine led to a mixture of allylic amines in 9 % yield. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Enantioseparation of amino acid amides on an (S)‐N‐(3,5‐dinitrobenzoyl)leucine‐N‐phenyl‐N‐propylamide‐bonded silica in normal phase CEC
Authors: Kim In Whan , Hyun Myung Ho , Gwon Jurim , Jin Juhyeon , Park Jung Hag 
Published: February 2009

Abstract(S)‐N‐(3,5‐Dinitrobenzoyl)leucine‐N‐phenyl‐N‐propylamide‐bonded silica was used as a chiral stationary phase for separation of enantiomers of some racemic π‐acidic and π‐basic amino acid amides in normal phase capillary LC (CLC) and CEC. For generation of EOF in CEC, different amounts of water were added to n‐hexane–isopropanol (IPA) eluents. Influences of added water and composition of polar modifier on retention, enantioselectivity and resolution were studied. Generally better separation was obtained in the eluents of lower water content. Shorter retention and better enantioselectivities were observed in the eluents of higher IPA content, whereas resolution became lower as IPA content was increased. Enantioselectivities were comparable but resolutions were much better in CEC than CLC.
Rapid determination of superoxide free radical in hepatocellular carcinoma cells by MCE with LIF
Authors: Liu Xin , Li Qingling , Gong Xiaocong , Li Hongmin , Chen Zhenzhen , Tong Lili , Tang Bo 
Published: February 2009

AbstractA method for determination of superoxide free radical (O2–•) based on MCE with LIF was developed. Fluorescent reagent 2‐chloro‐1, 3‐dibenzothiazolinecyclohexene, which was synthesized in our laboratory, was employed as the labeling reagent, the highest derivatization efficiency was obtained in 20 mM HEPES buffer (pH 7.4) for 10 min at 37°C. Optimal determination of O2–• was achieved on a glass microchip, using 50 mM HEPES buffer (pH 7.4). Under the optimized conditions, linearity of response was obtained in the range of 4.0×10−7–1.0×10−5 M, the detection limit (S/N=3) was 0.15 μM, the RSDs of migration time and peak area were 2.6 and 3.8%, respectively. Interference experiment was investigated and the result indicates that 1000‐fold molar excess of hydrogen peroxide does not interfere with the determination of O2–• in complex system. Finally, the method has been successfully applied to determine O2–• in hepatocellular carcinoma cells as well as phorbol 12‐myristate 13‐acetate stimulated RAW264.7 macrophages. The average recoveries were 97.3 and 98.6%, respectively.
Three‐dimensional behavior of a spherical self‐centering precast prestressed pile isolator
Authors: Jünemann Rosita , de la Llera Juan C. , Besa Jaime , Almazán José L. 
Published: February 2009

AbstractA 3D analytical formulation of a precast prestressed pile (PPP) seismic isolator with top and bottom spherical rolling kinematic constraints is proposed. The PPP isolator was initially conceived as a low‐cost seismic isolation (and foundation) system for housing units of low‐income people. Since these structures are usually located at sites with poor soil conditions, the PPP isolator also works as a foundation pile by connecting the superstructure with more competent soil layers. The non‐holonomic nature of the rolling constraint is dealt with by a structural formulation. The proposed 3D formulation is validated by numerical results obtained from a previously proposed formulation for the 2D problem, and a contact finite element model in ANSYS (www.ansys.com). Other issues associated with the dynamic response of isolated structures with the PPP are also examined, such as expected response reductions, variation in the axial force of the central prestressed cable, and torsional response amplifications. Finally, guidelines to estimate the actual 3D response using 2D analysis results are investigated. Copyright © 2009 John Wiley & Sons, Ltd.
Improving the inverse compensation method for real‐time hybrid simulation through a dual compensation scheme
Authors: Chen Cheng , Ricles James M. 
Published: February 2009

AbstractReal‐time hybrid simulation combines experimental testing of physical substructure(s) and numerical simulation of analytical substructure(s), and thus enables the complete structural system to be considered during an experiment. Servo‐hydraulic actuators are typically used to apply the command displacements to the physical substructure(s). Inaccuracy and instability can occur during a real‐time hybrid simulation if the actuator delay due to servo‐hydraulic dynamics is not properly compensated. Inverse compensation is a means to negate actuator delay due to inherent servo‐hydraulic actuator dynamics during a real‐time hybrid simulation. The success of inverse compensation requires the use of a known accurate value for the actuator delay. The actual actuator delay however may not be known before the simulation. An estimation based on previous experience has to be used, possibly leading to inaccurate experimental results. This paper presents a dual compensation scheme to improve the performance of the inverse compensation method when an inaccurately estimated actuator delay is used in the method. The dual compensation scheme modifies the predicted displacement from the inverse compensation procedure using the actuator tracking error. Frequency response analysis shows that the dual compensation scheme enables the inverse compensation method to compensate for actuator delay over a range of frequencies when an inaccurately estimated actuator delay is utilized. Real‐time hybrid simulations of a single‐degree‐of‐freedom system with an elastomeric damper are conducted to experimentally demonstrate the effectiveness of the dual compensation scheme. Exceptional experimental results are shown to be achieved using the dual compensation scheme without the knowledge of the actual actuator delay a priori. Copyright © 2009 John Wiley & Sons, Ltd.
Steady‐state heat flux measurements in radiative and mixed radiative–convective environments
Authors: Lam Cecilia S. , Weckman Elizabeth J. 
Published: February 2009

AbstractThe steady‐state responses of four heat flux gauges (Schmidt–Boelter, Gardon, directional flame thermometer (DFT) and hemispherical heat flux gauge (HFG)) were examined under various radiative and convective heating conditions. In radiative environments, Gardon measurements were up to 8% higher than Schmidt–Boelter measurements, but in mixed radiative–convective environments, Gardon measurements were 8–18% below those of the Schmidt–Boelter gauge. This difference increased as the convective portion of the total heat transfer increased, due to discrepancies between the radiation‐based calibration environment and the application environment. The DFT data in radiative environments were comparable with the Schmidt–Boelter and Gardon values (within 12%), with the difference largely attributed to natural convection losses from the DFT. In mixed environments, the DFT values were significantly lower than those of the Schmidt–Boelter gauge due to differences in the surface temperatures of the gauges, resulting in the convective flow cooling, rather than heating, the DFT. The HFG heat flux estimates were 35–48% lower than the Schmidt–Boelter measurements under radiative conditions, influenced by large conduction losses from the sensor plate to the gauge housing. Lateral conduction due to a mismatch between the experimental convective flow outlet diameter and the gauge width also affected results from the DFT and HFG. Copyright © 2009 John Wiley & Sons, Ltd.
Duloxetine in acute major depression: review of comparisons to placebo and standard antidepressants using dissimilar methods
Authors: Girardi Paolo , Pompili Maurizio , Innamorati Marco , Mancini Michele , Serafini Gianluca , Mazzarini Lorenzo , Del Casale Antonio , Tatarelli Roberto , Baldessarini Ross J. 
Published: February 2009

AbstractBackgroundRandomized controlled trials (RCTs) of duloxetine (DLX), an inhibitor of both norepinephrine and serotonin transporters (SNRI), have tested its efficacy in acute major depressive disorder (MDD) versus placebo (PBO) or standard serotonin‐reuptake inhibitors (SRIs) and require review, comparing analytical methods.MethodComputerized searching to identify reports of RCTs of DLX in adult, acute MDD patients permitted meta‐analytic pooling to estimate overall response and remission rates, to compare mixed‐model, repeated measures (MMRM) versus last‐observations‐carried‐forward (LOCF) analytical methods, and to assess relations of DLX dose to efficacy and adverse outcomes.ResultsWe identified 17 RCTs involving 22 comparisons (DLX versus PBO [n = 17) and DLX versus an SRI [n = 16]), based on MMRM and LOCF methods that allowed estimates of response (≥50% improvement of depression scores) or remission (final depression score ≤7). There was a large overall DLX/PBO contrast (LOCF, RR = 1.42 [CI: 1.31–1.53], p < 0.0001, with a success rate of 65% [11/17]), and somewhat larger effects with MMRM in both response (MMRM: RR = 1.48 [95%CI: 1.31–1.66] versus LOCF: RR = 1.41 [CI: 1.28–1.56]; NNT 4.8 versus 6.5) and remission (MMRM: RR = 1.61 [CI: 1.41–1.85] versus LOCF: RR = 1.44 [CI: 1.27–1.63]; NNT = 5.9 versus 8.9). Based on LOCF methods, dropout rates were similar with DLX and PBO (RR = 1.04 [CI: 0.94–1.15]); DLX response was dose‐dependent (r = +0.72, p = 0.001), and RCT‐dropout rates were inversely related to DLX dose, but possibly artifactually.LimitationsRCTs involving DLX are limited, with few direct comparisons to standard antidepressants.ConclusionsDLX has good evidence of efficacy in acute, adult MDD, especially at doses of 80–120 mg/day, but remains inadequately tested against standard alternatives. MMRM analyses yielded slightly superior FLX/PBO contrasts than older LOCF methods. Copyright © 2009 John Wiley & Sons, Ltd.
Proteomic analysis of apoptosis related proteins regulated by proto‐oncogene protein DEK
Authors: Kim Dong‐Wook , Chae Jung‐IL , Kim Ji‐Young , Pak Jhang Ho , Koo Deog‐Bon , Bahk Young Yil , Seo Sang‐Beom 
Published: February 2009

AbstractA nuclear phosphoprotein, DEK, is implicated in certain human diseases, such as leukemia and antoimmune disorders, and a major component of metazoan chromatin. Basically as a modulator of chromatin structure, it can involve in various DNA and RNA‐dependent processes and function as either an activator or repressor. Despite of numerous efforts to suggest the biological role of DEK, direct target proteins of DEK in different physiological status remains elusive. To investigate if DEK protein triggers the changes in certain protein networks, DEK was knocked down at both types of cell clones using siRNA expression. Here we provide a catalogue of proteome profiles in total cell lysates derived from normal HeLa and DEK knock‐down HeLa cells and a good in vitro model system for dissecting the protein networks due to this proto‐oncogenic DEK protein. In this biological context, we compared total proteome changes by the combined methods of two‐dimensional gel electrophoresis, quantitative image analysis and MALDI‐TOF MS analysis. There were a large number of targets for DEK, which were differentially expressed in DEK knock‐down cells and consisted of 58 proteins (41 up‐regulated and 17 down‐regulated) differentially regulated expression was further confirmed for some subsets of candidates by Western blot analysis using specific antibodies. In the identified 58 spots, 16% of proteins are known to be associated with apoptosis. Among others, we identified apoptosis related proteins such as Annexins, Enolase1, Lamin A, and Glutathione‐S‐transferase omega 1. These results are consistent with recent studies indicating the crucial role of DEK in apoptosis pathway. We further demonstrated by ChIP analysis that knock‐down of DEK caused hyperacetylation of histones around Prx VI promoter which is upregulated in our profile. Using immunoblotting analysis, we have demonstrated the modulation of other caspase‐dependent apoptosis related proteins by DEK knock‐down and further implicate its role in apoptosis pathway. J. Cell. Biochem. 106: 1048–1059, 2009. © 2009 Wiley‐Liss, Inc.