bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mid‐ and Far‐Infrared Marker Bands of the Metal Coordination Sites of the Histidine Side Chains in the Protein Cu,Zn‐Superoxide Dismutase
Authors: Xerri Bertrand , Petitjean Hugo , Dupeyrat François , Flament Jean‐Pierre , Lorphelin Alain , Vidaud Claude , Berthomieu Catherine , Berthomieu Dorothée 
Published: August 2014

AbstractVibrational spectroscopy gives important information on the properties of ligand and metal–ligand bonds in metalloenzymes. Infrared spectroscopy is appealing for the study of metal active sites that are not amenable to Raman spectroscopy. We present a combined experimental and theoretical approach to analyze the mid‐ and far‐IR spectra of Cu,Zn‐superoxide dismutase (Cu,Zn‐SOD) as a probe of the histidine ligands. This metalloenzyme provides a unique model to identify specific IR signatures of metal–histidine coordination and to study their alterations as a function of the metal (copper/zinc), the copper valence state (+I/+II), the histidine coordination mode (Nτ and Nπ) and the histidine protonation state. DFT calculations combined with normal mode descriptions from potential energy distribution calculations were performed on two slightly different cluster models. Differences in the constraints at the side chain of one histidine Cu ligand sensibly modify the geometric parameters and vibrational properties. Electrochemically induced FTIR difference spectroscopy provided mid‐ and far‐IR fingerprint spectra of the Cu protein in aqueous media that are sensitive to the redox state of the Cu centre at the active site. Comparisons of the DFT predictions with the experimental IR modes of the histidine ligands at the Cu,Zn‐SOD active site showed that useful mid‐IR markers of histidine Nτ and Nπ coordination were predicted with good accuracy. The DFT analysis further demonstrated a link between the ν(C4–C5) mode frequency of His46 and the specific properties of the His46–Cu bond in Cu,Zn‐SOD. A combined theoretical and experimental approach on samples in H2O and 2H2O or 15N‐labelled samples identified the contributions from the histidine side chain modes in the 669–629 cm–1 region.
Properties of an Indium Tin Oxide Electrode Modified by a Laser Nanostructured Thin Au Film for Biosensing
Authors: Grochowska Katarzyna , Siuzdak Katarzyna , Śliwiński Gerard 
Published: August 2014

AbstractStructural, optical, and electrochemical characteristics of the indium tin oxide (ITO) electrode modified by Au nanoparticle (NPs) produced by pulsed UV laser irradiation of thin films are investigated in this work. Properties of the NP arrays depend on the film thickness and parameters of the laser interaction. Semi‐regular structures characterized by broad size distributions of mean values ca. 62–92 nm are observed in the SEM images. In absorbance spectra the plasmon resonance peaks located around 544 nm reveal an IR shift and an increase of damping of the plasmonic enhancement with increasing NP size. Despite the broad size distribution and negative effect of damping that results in plasmon decay times of below 3.2 fs, the ITO electrode modified by Au NP arrays shows marked improvement of the electrochemical activity towards the Fe2+/Fe3+ redox couple and also glucose. Results obtained for non‐enzymatic glucose detection indicate the potential for cost‐effective solutions in the area of biosensing.
Rhodium‐Catalyzed Alkene Hydrosilylation via a Hydride Shuttle Process by Diene Ligands: Dramatic Enhancement of Regio‐ and Diastereoselectivity
Authors: Hua Yuanda , Nguyen Hiep H. , Trog Gabriela , Berlin Adam S. , Jeon Junha 
Published: August 2014

AbstractA cooperative ligand‐assisted, Rh‐catalyzed intramolecular alkene hydrosilylation of homoallylic silyl ethers (1) was developed to provide 1,3‐trans‐oxasilacyclopentanes (trans‐2) in a highly regio‐ and diastereoselective manner. The modification of metal‐ligand architecture employing an inner‐sphere functional diene ligand (1,3‐cyclohexadiene) and a supporting phosphine ligand (BINAP) was identified as responsible for dramatic enhancement of selectivities. Mechanistic details of a diene ligand‐mediated hydride shuttle process are presented as the potential mechanistic driving force behind the high level of the selectivities.
Organocatalytic Enantioselective Strecker Reaction of Imines Containing a Thiazole Moiety by Using a Cinchona‐Based Squaramide Catalyst
Authors: He Hai‐Xiao , Du Da‐Ming 
Published: August 2014

AbstractAn organocatalytic enantioselective Strecker reaction was developed for the synthesis of α‐amino nitriles that contain a thiazole moiety by using a cinchona‐based squaramide catalyst. The corresponding products were obtained in good to excellent yields (up to 99 %) with excellent enantioselectivities (up to 98 % ee) by starting from aromatic‐substituted imines. In addition, two trifunctional squaramides with amino acid residues were synthesized, and good enantioselectivities (up to 89 % ee) were achieved when they were employed in the model reaction.
Modular Syntheses of Star‐Shaped Pyridine, Bipyridine, and Terpyridine Derivatives by Employing Sonogashira Reactions
Authors: Trawny Daniel , Kunz Valentin , Reissig Hans‐Ulrich 
Published: August 2014

AbstractA simple and flexible synthesis for a series of star‐shaped pyridine, bipyridine, and terpyridine derivatives is reported by using a modular approach that combines the use of a ligand, spacer, and core unit. A fairly efficient method to prepare 4′‐nonafloxy‐functionalized terpyridine derivatives is described. The building blocks that contain the functionalized pyridine, bipyridine, or terpyridine derivatives were linked to different C3‐symmetrical core units. In most cases, Sonogashira reactions were employed in the crucial final steps of the synthesis. A star‐shaped dodecafluorinated compound was also prepared in a straightforward fashion. A simple procedure for the preparation of partially silylated 1,3,5‐triethynylbenzene derivatives is presented, which provides an approach to C2‐symmetrical star‐shaped compounds that have only one terpyridine and two terphenyl units as “dummy” ligands. The absorption and emission spectra of the fully conjugated C3‐symmetrical pyridine derivatives were systematically investigated, and fairly large Stokes shifts were observed.
Repetitive transcranial magnetic stimulation in neuropathic pain secondary to malignancy: A randomized clinical trial
Authors: Khedr E.M. , Kotb H.I. , Mostafa M.G. , Mohamad M.F. , Amr S.A. , Ahmed M.A. , Karim A.A. , Kamal S.M.M. 
Published: August 2014

AbstractBackgroundSignificant analgesic effects of repetitive transcranial magnetic stimulation (rTMS) have been found in several studies of patients with chronic pain of various origins, but never for malignancy. The objective of this study was to assess the efficacy of 10 sessions of rTMS over the primary motor cortex (M1) in patients suffering from malignant neuropathic pain.MethodsThirty‐four patients were randomly allocated into one of two groups to receive real (20 Hz, 10 s, 10 trains with 80% intensity) or sham rTMS daily for 10 consecutive days. Patients were evaluated using a verbal descriptor scale (VDS), a visual analogue scale (VAS), Leeds assessment of neuropathic symptoms and signs (LANSS) and Hamilton rating scale for depression (HAM‐D) at baseline, after the first, fifth and 10th treatment sessions, and then 15 days and 1 month after treatment.ResultsThere were no significant differences between real and sham groups in the duration of illness or pain rating scores at the baseline. A significant ‘Time × Group’ interaction was recorded indicating that real and sham rTMS had different effects on the VDS, VAS, LANSS and HAM‐D scales. Post‐hoc testing showed that the group of patients treated with real rTMS had greater improvement in all scales that persisted up to 15 days, but were not present 1 month later. Significant positive correlations between the percentage of pain reduction and HAM‐D after the 10th session and 15 days later were recorded.ConclusionThe results demonstrate that 10 rTMS sessions over the M1 can induce short‐term pain relief in malignant neuropathic pain.
Amorphous Li4Ti5O12 Thin Film with Enhanced Lithium Storage Capability and Reversibility for Lithium‐Ion Batteries
Authors: Yu Zhaozhe , Zhu Guisheng , Xu Huarui , Yu Aibing 
Published: August 2014

AbstractThis manuscript focuses on how to improve the electronic conductivity and lithium‐ion diffusivity of Li4Ti5O12 thin films, which present a serious constraint to the development of the solid‐state lithium‐ion batteries. Given this understanding, we have found that creating amorphous structural features and hierarchical channels of thin films form a very simple yet effective approach to solve the problem. The unique structural features and high electrical conductivity of the as‐prepared thin films result in high capacity (283.5 mAh g−1 at 10 μA cm−2) and good cyclic stability (≈3 % capacity loss after 100 cycles at 10 μA cm−2). These important findings could open up new opportunities for Li4Ti5O12 in constructing high‐performance binder‐free energy storage devices.
Iterative Stochastic Elimination for Solving Complex Combinatorial Problems in Drug Discovery
Authors: Stern Noa , Goldblum Amiram 
Published: August 2014

AbstractIterative Stochastic Elimination (ISE) is a novel algorithm that was originally developed to solve extremely complex problems in protein structure and interactions, and has since been applied to diverse topics that share a few general “ingredients”: they are extremely complex, of combinatorial nature, may be presented as large sets of variables that can each have many alternative values, there is some interdependence of the variables on each other, and there is a scoring function that can evaluate each choice of the problems “configuration”; this is the set of single values of each of the variables that constitute its full presentation. Those are picked randomly in a large sample, the analysis of which allows decisions to be made for rejecting some values for each of the variables; thus resulting in a smaller set of potential combinations. This continues in iterations until the number of combinations allows all the remaining options to be computed exhaustively and to order them by their scores. ISE has been mainly applied to problems that are relevant to drug design and discovery. We demonstrate, among others, the use of ISE to determine the properties of molecular ensembles and to pick the best molecules (“focused libraries”) for hitting a specific target. Future ideas for using ISE are discussed, as well as mentioning its contributions to the construction of two start‐up companies.
The “Monkey‐Bar” Mechanism for Searching for the DNA Target Site: The Molecular Determinants
Authors: Vuzman Dana , Levy Yaakov 
Published: August 2014

AbstractDNA recognition by DNA‐binding proteins, which is a pivotal event in most gene regulatory processes, is often preceded by an extensive search for the correct site. A facilitated diffusion process, in which a DBP combines 3D diffusion in solution with 1D sliding along DNA, has been suggested to explain how proteins can locate their target sites on DNA much faster than predicted by 3D diffusion alone. One of the key mechanisms in the localization of the target by a DNA‐binding protein is intersegment transfer in which the protein forms a bridged intermediate between two distant DNA regions. This jumping mechanism is more enhanced when the DNA‐binding protein is asymmetric in its structure or its dynamics. We suggest that asymmetry supports the “monkey bar” mechanism, in which different domains of the protein interact with different DNA regions. In this minireview, we discuss how the molecular architectures of the proteins and DNA may modulate the efficiency of monkey bar dynamics.
A SOUTH AFRICAN STUDY ON CAREGIVER PERCEPTIONS OF A PARENT–INFANT INTERVENTION IMPLEMENTED TO FOSTER SECURE ATTACHMENT
Authors: Aspoas Belinda , Amod Zaytoon 
Published: August 2014

ABSTRACTCommunity‐based interventions that support the parent–infant dyad present an ideal opportunity to help foster secure attachment relationships. This study set out to investigate a parent–infant intervention that was implemented in a peri‐urban township in South Africa. The aim of the research was to understand caregivers’ experience of this intervention and shed light on why some caregivers make optimal use of this intervention whereas others do not. Data for this study were collected by holding a focus group with 11 caregivers, who were selected using purposive sampling. The discussion that took place in the group was video‐recorded and transcribed verbatim. Thematic content analysis of this data indicates that caregivers are very receptive to the intervention, which they see in the role of “grandmother.” Yet, their socially and economically weak position hinders them from making full use of the intervention. Ideally, they want professionals to reach out to them. This research highlights how important it is for early parent–infant interventions to move beyond the consulting room and to meet caregivers on their terms.
NOTE ON CONSTRUCTION OF AN ITEM ANALYSIS TABLE FOR THE HIGH‐LOW‐27‐PER‐CENT GROUP METHOD
Authors: Fan C. T. 
Published: August 2014

ABSTRACTThis paper describes the construction of a new item analysis table for the high‐low‐27‐per‐cent group method. The table provides a ready means of translating the observed proportions of success in the two extreme groups (pH, pL) into measures of item difficulty and item discrimination (p, Δ, and r). The tabled values of both the difficulty index, p, and the discrimination index, r, have been derived from Karl Pearson's tables of the normal bivariate surface.
GROUP INFLUENCE ON INDIVIDUAL RISK TAKING1
Authors: Wallach Michael A. , Kogan Nathan , Bem Daryl J. 
Published: August 2014

ABSTRACTDoes group interaction lead to greater conservatism or to greater risk taking in decisions than would obtain were the decisions arrived at individually.–or is there an averaging effect? This question was investigated with a procedure in which the protagonist in each of 12 everyday life situations must choose between two courses of action, one of which involves considerably more risk than the other but also is much more rewarding if successful. The S must decide on the lowest level of probability for the success of the risky alternative that he would deem sufficient to warrant its choice.A total of 218 liberal arts university students participated in the study. In the experimental condition, the Ss first arrived at individual decisions concerning each of the 12 situations; then, they were brought together in discussion groups of six with the request that they reach a group consensus on each decision; and afterward, they were asked to make all their decisions privately once again. Some Ss also made private decisions yet another time two to six weeks later. The group members' judgments of one another's relative degrees of influence and of popularity within the group also were obtained. There were 14 all‐male and 14 all‐female groups. In the control condition, Ss made their decisions individually each of two times with one week intervening, under instructions the second time that encouraged them to change rather than simply to recall their earlier decisions.It was found that (1) group decisions exhibit greater risk taking than appears in pre‐discussion individual decisions; (2) post‐discussion private decisions exhibit the same increase in risk taking as occurs in the group decisions; (3) the increase in risk taking resulting from the discussion process is still maintained after a subsequent period of two to six weeks has elapsed; (4) no shift in risk taking level occurs over time in the absence of the discussion process; and (5) degree of risk taking in pre‐discussion individual decisions and degree of judged influence within the group are positively related. Two interpretations of these findings were suggested, either or both of which may apply: (1) the knowledge that one's decisions are being made jointly with others leads to a diffusion of personal responsiblity, the outcome of which is an increased willingness to take risks; (2) high risk takers are more likely to take the initiative in social situations, with the result that they become more influential in the group.
SOME IMPLICATIONS OF TESTING PROCEDURES FOR AUTO‐INSTRUCTIONAL PROGRAMMING
Authors: Grether Walter F. 
Published: August 2014

ABSTRACTAlthough there are fundamental differences in the objectives of the two activities, the programming of instructional material bears many similarities to the construction of tests. A systematic comparison of problems and procedures reveals important implications for programming from the older field of testing. Theory and experience in test construction can be especially useful in the selection of valid criteria for assessing the effectiveness of a program, the ordering of instructional subject matter, the writing of instructional frames, and the formal evaluation of the program. Adaptive programming implies measurement of both aptitude and achievement in order to assign trainees to appropriate individual sequences of instruction. Possible applications resulting from examination of these and other issues are explored, and necessary further research is suggested.
A NOTE ON SOCIAL DESIRABILITY RESPONSE STYLE AND LEARNING
Authors: Stricker Lawrence J. 
Published: August 2014

ABSTRACTIn Brown's study of the learning of personality items which were paired with nonsense syllables, a major finding was that social desirability response style was related to learning measures for women but not men. A reanalysis of these results found that social desirability response style was related to delayed recall for both men and women, and confidence and immediate recall for women only. It was not related to trials to mastery, learning time, and blockings.It was concluded that this study partially supports Edwards' social desirability response style reinterpretation of studies of anxiety and learning, but that many previous studies do not.
DIMENSIONS OF ANALYTIC ATTITUDE IN COGNITION AND PERSONALITY1
Authors: Messick Samuel , Fritzky Ferdinand J. 
Published: August 2014

ABSTRACTA group‐administered procedure was developed to measure facility in learning complex designs with sufficient articulation to identify subsequent variations on the designs. Scores for 11 types of design variations and a group measure of embedded‐figures performance were intercorrelated and factor analyzed, producing four factors. The two major dimensions corresponded to facility in identifying (a) variations containing figural elements and (b) variations displaying figural form without elements. A third mode of stimulus analysis reflected the utilization of background information and was substantially correlated with the other two. A significant relationship was obtained between the element articulation factor and embedded‐figures performance, thereby linking element articulation to the field‐independent type of analytical functioning described by Witkin et al. (1962). The personality and cognitive correlates of these articulation scores were discussed in terms of analytic and relational categorizing as formulated by Kagan et al. (1962).
GAME INTERACTIONS WITH “HUMANS” AND “MACHINES” AND THEIR RELATIONS TO TACTICAL BEHAVIOR AND SUCCESS1
Authors: Myers Albert E. , Gibb Cecil A. , McConville Carolyn B. 
Published: August 2014

ABSTRACTAn experiment was performed in which Ss engaged in a “Path and Obstacles” game where the S had the task of tracing a path on a 5 times 5 plugboard in such a way as to avoid hitting any of the five obstacles that had been placed by the other player. Half the Ss were told that the other player was a machine which had been programmed to play the game and the other half were led to believe that they were playing against another human. In addition, half the players were told to compete against the other player while half were told to cooperate. In every instance the setting of the obstacles by the other player was determined by a prearranged plan. In the Human condition the other player was an accomplice who played according to a prearranged plan; the same plans, which determined the placement of every obstacle on every trial, were used in the Machine condition.Two strategies of obstacle placement were used. One, called the Fixed Path strategy, moved the obstacles in such a way as to never block one certain path. The trial to trial movement of the obstacles was basically random. The other strategy, called the Variable Path strategy, did not move the obstacles randomly from trial to trial, but rather in a highly systematic way. Whereas the Fixed Path strategy encouraged the S to use the same path repeatedly, the Variable Path strategy could not be solved by repetition. The latter encouraged the S to find a principle which was responsible for the movement of the obstacles.Striking differences in success were found. The Ss performed much better when their competitive opponent was a “machine” than they did when he was a “human.” On the other hand, cooperation with “humans” was significantly more successful than cooperation with “machines.”It was concluded that an S's expectations concerning the other player are a critical element in determining whether his performance on the task will be affected by a “human” or “machine” other. It was also tentatively concluded that “human” others induced more irrationality than “machine” others.
RELATIONSHIP OF AN INDEPENDENT ACTIVITIES QUESTIONNAIRE TO PERFORMANCE DURING HIGH SCHOOL
Authors: Schultz Charles B. , Skager Rodney W. 
Published: August 2014

ABSTRACTThe Independent Activities Questionnaire (IAQ) was developed as a measure of self‐initiated activity of high intellectual quality. Evidence for validity is presented in the form of correlations between IAQ response and measures of ability, interests, grades, activity level and initiative. The relatively low intercorrelation and differential validities of three a priori scales representing different content areas encourage further scale development. Frequencies of endorsement of the items were examined so that items can be revised to represent truly outstanding activities.
DIFFUSION OF RESPONSIBILITY AND LEVEL OF RISK TAKING IN GROUPS1
Authors: Wallach Michael A. , Kogan Nathan , Bem Daryl J. 
Published: August 2014

ABSTRACTThis study reports evidence supporting the following propositions: (1) Group discussion and consensus concerning decisions that involve actual risk ana payoffs lead to greater risk taking than occurs in the absence of such discussion and consensus. (2) The mechanism that underlies this group‐induced shift toward greater risk taking consists of a diffusion or spreading of responsibility. Using risks and payoffs based on monetary gain and loss for problem‐solving performance, the above propositions received strong confirmation for male college subjects. The results of various experimental manipulations provided positive support for viewing diffusion of responsibility as the causal factor at work.