bluuebunny/crossref_metadata_2025_split huggingface dataset:
Naphthobipyrrole‐Derived Sapphyrins: Rational Synthesis, Characterization, Nonlinear Optical Properties, and Excited‐State Dynamics
Authors: Sarma Tridib , Anusha Puliparambil Thilakan , Pabbathi Ashok , Venugopal Rao Soma , Panda Pradeepta K. 
Published: September 2014

AbstractTwo new free‐base β‐octa and hexaalkyl naphthobipyrrole‐derived sapphyrins are reported along with various salts thereof. One of them has substituents at all of its β positions, whereas the pyrrole unit opposite to the bipyrrolic moiety is unsubstituted in the other. The effect of bipyrrole fusion on the structure of sapphyrins was explored. Interestingly, an unprecedented sandwiched supramolecular aqua‐bridged free‐base sapphyrin dimer was also characterized in the solid state. Further, the effect of anions on the third‐order nonlinear optical properties of these sapphyrins were explored in the salt form, along with their detailed excited‐state dynamics by both degenerate and nondegenerate pump–probe studies.
High Performance Photoinitiating Systems for Holography Recording: Need for a Full Control of Primary Processes
Authors: Ibrahim Ahmad , Allonas Xavier , Ley Christian , Kawamura Koichi , Berneth Horst , Bruder Friedrich‐Karl , Fäcke Thomas , Hagen Rainer , Hönel Dennis , Rölle Thomas , Walze Guenther , Weiser Marc Stephan 
Published: September 2014

AbstractOptimization of holography recording in photopolymers was studied from the point of view of a quite general process, that is, the photogeneration of radicals. On the basis of a dye/coinitiator photoinitiating system, the effect of primary events and their relative efficiency was investigated with respect to the final overall properties, such as the diffraction efficiency. Quenching of the dye excited states by the borate salts coinitiators exhibits important differences depending on the dye used (Rose Bengal or Safranine O). Keeping in mind that both singlet and triplet states of the dyes can react, and taking into account the viscosity of the matrix, a method to evaluate the overall quantum yield of radicals released is proposed. It is found that this quantum yield well correlates with the maximum rate of photopolymerization. More interestingly, the dose required to obtain a given diffraction efficiency was found to be also governed by the radical quantum yield, showing that the final property is directly governed by primary events. This shed some light on the efficiency of photochemical pathway to generate radicals for use in organic or polymer areas.
Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances
Authors: Sannicolò Francesco , Mussini Patrizia R. , Benincori Tiziana , Cirilli Roberto , Abbate Sergio , Arnaboldi Serena , Casolo Simone , Castiglioni Ettore , Longhi Giovanna , Martinazzo Rocco , Panigati Monica , Pappini Marco , Quartapelle Procopio Elsa , Rizzo Simona 
Published: September 2014

AbstractLinear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain‐end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an “inherently chiral” sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability.
Coupled‐Cluster Interaction Energies for 200‐Atom Host–Guest Systems
Authors: Andrejić Milica , Ryde Ulf , Mata Ricardo A. , Söderhjelm Pär 
Published: September 2014

AbstractWe have developed a method to calculate interaction energies of large systems (such as host–guest or even protein–ligand systems) at the local coupled‐cluster with singles, doubles, and perturbative triples level, and with extrapolation to the limit of a complete basis set. The method is based on the polarizable multipole interactions with supermolecular pairs molecular fractionation approach, which combines a pairwise quantum‐mechanical evaluation of the short‐range interactions with a polarizable multipole treatment of many‐body effects. The method is tested for nine guest molecules binding to an octa‐acid host (in total 198–207 atoms), as part of the SAMPL4 blind challenge. From the test calculations, the accuracy of the approach is found to be 10 kJ mol−1 or better. Comparison with dispersion‐corrected density functional theory reveals that the latter underestimates the dispersion contribution for this type of system, which leads to a difference in the ranking of the ligands.
Red Blood Cells Polarize Green Laser Light Revealing Hemoglobin′s Enhanced Non‐Fundamental Raman Modes
Authors: Marzec Katarzyna M. , Perez‐Guaita David , de Veij Marleen , McNaughton Don , Baranska Malgorzata , Dixon Matthew W. A. , Tilley Leann , Wood Bayden R. 
Published: September 2014

AbstractIn general, the first overtone modes produce weak bands that appear at approximately twice the wavenumber value of the fundamental transitions in vibrational spectra. Here, we report the existence of a series of enhanced non‐fundamental bands in resonance Raman (RR) spectra recorded for hemoglobin (Hb) inside the highly concentrated heme environment of the red blood cell (RBC) by exciting with a 514.5 nm laser line. Such bands are most intense when detecting parallel‐polarized light. The enhancement is explained through excitonic theory invoking a type C scattering mechanism and bands have been assigned to overtone and combination bands based on symmetry arguments and polarization measurements. By using malaria diagnosis as an example, we demonstrate that combining the non‐fundamental and fundamental regions of the RR spectrum improves the sensitivity and diagnostic capability of the technique. The discovery will have considerable implications for the ongoing development of Raman spectroscopy for blood disease diagnoses and monitoring heme perturbation in response to environmental stimuli.
Cyclizations of Aryl Enynes Containing Propargyl Alcohol and Diallylamine Groups to Yield Indolecarbaldehydes Induced by Ruthenium Complexes
Authors: Feng Yi‐Jhen , Tsai Fu‐Yuan , Huang Shou‐Ling , Liu Yi‐Hong , Lin Ying‐Chih 
Published: September 2014

AbstractThe reactions of RuCl(PPh3)2Cp ([Ru]Cl, Cp = cyclopentadienyl) with aryl enynes 1a–1c containing propargyl alcohol and diallylamine groups on the aryl ring give the carbene complexes 2a–2c, each of which contains an indole group. With an additional methylene group, the aryl enyne 1d reacts with [Ru]Cl to afford the dihydroisoquinoline complex 3d. For 1a–1d, the C–N bond‐forming process occurs when the triple bond is π‐coordinated to the metal center. The reaction of [Ru]Cl with the aryl enyne 1e containing an isoxazole group affords the carbene complex 2e by a C–C bond formation between the isoxazole group and C‐β of the triple bond, accompanied by the opening of the isoxazole ring. The reactions of 2a–2c and 2e with O2/NEt3 are assisted by visible light to afford the corresponding aldehydes 4a–4c and 5e. From DFT calculations, visible light results in the partial population of the lowest unoccupied molecular orbital (LUMO), which has Ru=C antibonding character; therefore, the bond is weakened, and the oxygenation/demetallation reactions are slightly promoted.
Synthesis of Furans through Silver‐Catalyzed Propargyl–Claisen Rearrangement Followed by Cyclocondensation
Authors: Palisse Adeline , Kirsch Stefan F. 
Published: September 2014

AbstractThe generation of highly substituted furans from propargyl vinyl ethers bearing a free hydroxy group was investigated. In the presence of catalytic amounts of AgBF4, a formal [3,3] sigmatropic rearrangement takes place in the first stage of the sequence. The resulting allenyl carbonyl intermediates then undergo cyclocondensation, which upon double‐bond isomerization leads directly to the five‐membered heterocyclic products. This domino reaction allows the synthesis of various tri‐ and tetrasubstituted furan products; an example leading to pyrroles in an analogous way is also described.
Fundamentals and Modeling of Electrokinetic Transport in Nanochannels
Authors: Yeh Hung‐Chun , Wang Moran , Chang Chih‐Chang , Yang Ruey‐Jen 
Published: September 2014

AbstractWhen the channel size approaches the thickness of the charged layer (typically, ∼10–100 nm), the resulting molecular and non‐equilibrium effects are markedly different from those observed in larger channels and have a significant effect on the transport behavior of solutes and solvents. As a result, the problem of modeling fluidic behavior at the nanoscale has attracted increasing interest in recent years. This review introduces the fundamental theories and principles associated with electrokinetic transport and molecular dynamics modeling, and discusses various applications of nanofluidic devices in the physics, mechanics, and chemistry fields.
Directed Evolution of Artificial Metalloenzymes
Authors: Ilie Adriana , Reetz Manfred T. 
Published: September 2014

AbstractTransition metal catalysis in asymmetric transformations plays a pivotal role in modern synthetic organic chemistry, with these catalysts being tuned by systematic variation of the chiral ligand. More than three decades ago it was recognized that an alternative approach is possible, namely the anchoring of an achiral ligand/metal entity in an appropriate protein host, with formation of an artificial metalloenzyme (hybrid catalyst). However, this procedure delivers a single transition metal catalyst, with high enantioselectivity being a matter of chance. In view of this restriction, we proposed in 2001/2002 the concept of directed evolution of such hybrid catalysts. The most intensively studied system involves biotinylated phosphine/metal entities which are non‐covalently anchored to streptavidin. The present review summarizes progress in this intriguing area of research. It includes the assessment of the requirements of a given Darwinian system to be successful, and offers hints on how to achieve success in future studies.
DEVELOPING ABILITIES AND KNOWLEDGE: STYLE IN THE INTERPLAY OF STRUCTURE AND PROCESS
Authors: Messick Samuel 
Published: September 2014

ABSTRACTAs commentary for a special issue on Education and Human Ability of the British journal Educational Analysis, two recurrent themes in the volume are underscored as well as three critical educational issues that were addressed only peripherally there. The two recurrent themes deal with the roles of knowledge and of context in school learning. The three peripheral issues given central focus in the commentary are (1) the role of schooling in the development of cognitive abilities and of developed abilities in the processes of school learning; (2) the role of cognitive styles as characteristic modes of organization and regulation in information processing which afford unifying self‐consistency in learning; and, (3) the problem of the match between features of the instruction and functional characteristics of the learner. The commentary thus centers on some of the salient roles in education and learning of knowledge, abilities, context, and style – especially as they merge in the problem of the match.
EFFECTS ON SCORE DISTRIBUTIONS OF DELETING AN UNKEYABLE ITEM FROM A TEST
Authors: Dorans Neil J. 
Published: September 2014

ABSTRACTThe purpose of this report is to present a formal analysis of the effects of item deletion on equating/scaling functions and reported score distributions. The phrase “item deletion” shall be used to refer to the process of changing the original key of a flawed item to either all options correct, including omits, or to no options correct, i.e., not scoring the flawed item. There are two aspects to the present analysis. The first aspect is analytical, focusing on the development of a formal model for the item deletion effect by decomposing it into its constituent elements. The second component of the analysis is empirical, involving the use of actual data to illustrate and supplement the analytical results. The analytical decomposition demonstrates how the effects of item properties, test properties, individual examinee responses and rounding rules combine to produce the item deletion effect on the equating/scaling function and candidate scores. In addition to demonstrating how the deleted item's psychometric properties can affect the equating function, the analytical component of the report examines the effects of not scoring vs. scoring all options correct and the effects of re‐equating vs. not re‐equating, as well as the interaction between the decision to re‐equate or to not re‐equate and the scoring option chosen for the flawed item. The empirical portion of the report uses data from the May 1982 administration of the SAT, which contained the circles item, to illustrate the effects of item deletion on reported score distributions and equating functions. The empirical data verify what the analytical decomposition predicts.
A REVIEW OF RESEARCH ON THE PREDICTION OF ACADEMIC PERFORMANCE AFTER THE FRESHMAN YEAR
Authors: Wilson Kenneth M. 
Published: September 2014

ABSTRACTThe criterion most frequently used in studies designed to assess the predictive validity of measures used in college admission has been the freshman‐year GPA. It is not self‐evident that the first‐year GPA provides either a sufficient or a representative sample of a student's academic performance. Questions have been raised regarding the validity of admissions measures for predicting longer‐term performance in college. This is the report of a systematic review of research bearing on (a) the validity of admissions measures for predicting GPA that reflects performance beyond the freshman year—i.e., longer‐term cumulative or independently computed post‐freshman‐year GPA, such as senior‐year GPA; (b) the comparative relevance and utility of freshman‐year, cumulative, and independently computed post‐freshman‐year GPA as criteria for the validation of admissions measures. Among other things, the research reviewed lends support to the traditional practice of employing the freshman‐year GPA in admissions‐related predictive validity studies.
SURVEY OF ACADEMIC WRITING TASKS REQUIRED OF GRADUATE AND UNDERGRADUATE FOREIGN STUDENTS
Authors: Bridgeman Brent , Carlson Sybil 
Published: September 2014

ABSTRACTA survey of the academic writing skills needed by beginning undergraduate and graduate students was conducted. Faculty, in 190 academic departments at thirty‐four U.S. and Canadian universities with high foreign student enrollments completed the questionnaire. At the graduate level, six academic disciplines with relatively high numbers of nonnative students were surveyed: business management (MBA), civil engineering, electrical engineering, psychology, chemistry, and computer science. Undergraduate English departments were chosen to document the skills needed by undergraduate students.The major findings are summarized below.

Although writing skill was rated as important to success in graduate training, it was consistently rated as even more important to success after graduation.
Even disciplines with relatively light writing requirements (e.g., electrical engineering) reported that some writing is required of first‐year students.
The writing skills perceived as most important varied across departments.
Faculty members reported that, in their evaluations of student writing, they rely more on discourse‐level characteristics than on word‐ or sentence‐level characteristics.
Discourse‐level writing skills of natives and nonnatives were perceived as fairly similar, but significant differences between natives and nonnatives were reported for sentence‐ and word‐level skills and for overall writing.
Among the ten writing sample topic types provided, preferred topic types differed across departments.
Although some important common elements among the different departments were reported, the survey data distinctly indicate that different disciplines do not uniformly agree on the writing task demands and on a single preferred mode of discourse for evaluating entering undergraduate and graduate students.
CONFIDENCE ENVELOPES FOR ITEM RESPONSE THEORY
Authors: Thissen David , Wainer Howard 
Published: September 2014

ABSTRACTA statistical method is described and illustrated which provides confidence envelopes around item response functions. Examples of 95% confidence envelopes for the one‐, two‐, and three‐parameter logistic response models are given.In addition, we describe, N‐line plots, which show the genesis of the envelope as well as the density of lines in the confidence region. These too are illustrated for the one‐, two‐, and three‐parameter logistic models.
STYLES, READING STRATEGIES AND TEST PERFORMANCE: A FOLLOW‐UP STUDY OF BEGINNING READERS
Authors: Chittenden Edward A. 
Published: September 2014

ABSTRACTFollow‐up data consisting of teacher ratings and reading achievement scores (CAT) were collected for twenty children whose early reading progress had been extensively documented in previous observational research. The children in the Follow‐up sample represented two contrasting stylistic groups with distinctive strategies for reading. The data indicated no difference between the groups in general reading ability by the end of the primary grades. There was evidence, however, of stylistic influences on children's responses to measures (subtests) of reading comprehension. Children who broadly relied upon anticipation of meanings, as their entry into text, exhibited reading strategies that were not well suited to constraints of comprehension items, whereas the children whose styles of learning were more linear and more narrowly focused exhibited strategies that were better matched to the task.
ESTIMATING THE IMPUTED SOCIAL COST OF ERRORS OF MEASUREMENT*
Authors: Lord Frederic M. 
Published: September 2014

ABSTRACTIf a loss function is available specifying the social cost of an error of measurement in the score on a unidimensional test, an asymptotic method, based on item response theory, is developed for optimal test design for a specified target population of examinees. Since in the real world such loss functions are not available, it is more useful to reverse this process; thus a method is developed for finding the loss function for which a given test is an optimally designed test for the target population. An illustrative application is presented for one operational test.
THE ROLE OF GRE GENERAL AND SUBJECT TEST SCORES IN GRADUATE PROGRAM ADMISSION
Authors: Oltman Philip K. , Hartnett Rodney T. 
Published: September 2014

ABSTRACTTo learn more about graduate program selectivity, admission test requirements, and the role the Graduate Record Examinations play in the admission process, a two‐phase study was carried out. First, the GRE® General Test and/or Subject Test requirements of a broad range of graduate programs were summarized by examining data in two issues of the Graduate Programs and Admissions Manual. Analyses of these data indicated how many and what kinds of graduate programs do and do not require or recommend GRE test scores. Second, a mail survey of graduate programs was carried out in order to determine their perceptions of the role test scores play in the admission process and to obtain specific information about how they use test score information. The same questionnaire (with appropriate branching instructions) was used to learn why certain programs do not require or recommend GRE scores. The following conclusions were reached:

While variations exist across disciplines, approximately 64 percent of all graduate programs require or recommend submission of GRE scores.
GRE test score requirements have not changed appreciably over the last decade.
There is little relationship between program selectivity and use of GRE scores.
The primary use of GRE scores appears to be to compensate for otherwise weak applicant credentials.
The primary reason given for not using GRE scores is that the departments feel that other data provide an adequate basis for admission decisions.
Graduate departments assign the most importance to undergraduate grades in making admission decisions, followed by letters of recommendation and by GRE scores, with other criteria rated progressively less important.
ANALYSIS OF SCORE CHANGE PATTERNS OF EXAMINEES REPEATING THE GRADUATE RECORD EXAMINATIONS GENERAL TEST1
Authors: Kingston Neal , Turner Nancy 
Published: September 2014

ABSTRACTThe stability of scores over time of the GRE® General Test verbal, quantitative, and analytical measures were studied using data from the self‐selected group of repeaters. Overall, in these analyses the new‐format GRE verbal measure demonstrated the greatest stability over time and the new‐format analytical measure the least.
ETHNIC, SOCIOECONOMIC, AND HOME LANGUAGE INFLUENCES UPON EARLY PERFORMANCE ON MEASURES OF ABILITIES
Authors: Laosa Luis M. 
Published: September 2014

ABSTRACTThe study examined both the levels and the profiles of performance on measures of various abilities by children from Chicano and non‐Hispanic White families of diverse socioeconomic levels, home language backgrounds, and family sizes. Measures were obtained when the children (N = 171) were 2 years and 6 months of age. Five ability areas were studied: verbal, reasoning, quantitative, memory, and motor–measured by the McCarthy Scales of Children's Abilities. Results revealed ethnic group differences in both (a) the absolute levels of performance in some ability areas and (b) the shapes of the profiles formed by the configuration of performance across the various ability areas. These ethnic group differences in performance were explained (statistically) on the basis of a combination of effects associated with ethnic group differences in socioeconomic status and home language.
RESPONSE TO CHANGING ASSESSMENT NEEDS: REDESIGN OF THE NATIONAL ASSESSMENT OF EDUCATIONAL PROGRESS
Authors: Messick Samuel 
Published: September 2014

ABSTRACTTo improve the interpretability, comparability, timeliness, and policy relevance of the results within fixed budgets, the new design for NAEP moves to a biennial schedule assessing four subject‐matter areas in each wave. Reading is assessed in every wave to provide timely reporting of trends in a basic area and to calibrate alternate cohorts; writing is assessed every other wave (4 years), as are math and science in alternate waves. In addition to the traditional assessment of 9‐, 13‐, and 17‐year olds, sampling is expanded to permit reporting of the associated modal grades (with redefined age definitions, the grades are 3, 7, and 11). There are thus four years intervening between subject assessments, age levels, and grade levels, thereby introducing a systematic cohort matching procedure. Balanced‐incomplete spiralling of exercises, as well as of background and program variables, permits the estimation of intercorrelations among all variables. This facilitates dimensional analyses within and across subject areas; item‐response scaling to improve comparability of scale meaning across ages, population groups, and time periods; and, the examination and structural analysis of various policy relevant correlates of educational performance.
A COMPUTER PROGRAM FOR SIMULATION EVALUATION OF IRT ABILITY ESTIMATORS
Authors: Thissen David , Wainer Howard , Rubin David 
Published: September 2014

ABSTRACTThis report documents the computer program which implements the design of our evaluation by simulation of IRT ability estimators (Wainer and Thissen, 1984). The program is reproduced in Appendix A and a sample of its main output file is Appendix B. It is printed here to facilitate the use of any or all of its routines in future investigations.