Individual word and phrase frequency effects in collocational processing: Evidence from typologically different languages, English and Turkish.

Collocations are understood to be integral building blocks of language processing, alongside individual words, but thus far evidence for the psychological reality of collocations has tended to be confined to English. In contrast to English, Turkish is an agglutinating language, utilizing productive morphology to convey complex meanings using a single word. Given this, we expected Turkish speakers to be less sensitive to phrasal frequencies than English speakers. In Study 1, we conducted a corpus analysis of translation-equivalent adjective-noun collocations (e.g., front door) and found differences between the two languages in frequency counts. In Study 2, we conducted a reaction time experiment to determine the sensitivity of native speakers of English and Turkish to the frequency of adjectives, nouns, and whole collocations. Turkish speakers were less sensitive to whole-phrase frequencies, as predicted, indicating that collocations are processed less holistically in Turkish than English. Both groups demonstrated that processing collocations involves combining information about individual words and phrases. Taken together, we show that speakers are sensitive to frequency information at multiple grain sizes that are attuned to the typology of different languages. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Corpus linguistics and clinical psychology: Investigating personification in first-person accounts of voice-hearing.

Triangulating corpus linguistic approaches with other (linguistic and non-linguistic) approaches enhances "both the rigour of corpus linguistics and its incorporation into all kinds of research" (McEnery & Hardie, 2012:227). Our study investigates an important area of mental health research: the experiences of those who hear voices that others cannot hear, and particularly the ways in which those voices are described as person-like. We apply corpus methods to augment the findings of a qualitative approach to 40 interviews with voice-hearers, whereby each interview was coded as involving 'minimal' or 'complex' personification of voices. Our analysis provides linguistic evidence in support of the qualitative coding of the interviews, but also goes beyond a binary approach by revealing different types and degrees of personification of voices, based on how they are referred to and described by voice-hearers. We relate these findings to concepts that inform therapeutic interventions in clinical psychology.

NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host-guest systems.

Nuclear magnetic resonance (NMR) lineshape analysis is a powerful tool for the study of chemical kinetics. Here we provide techniques for analysis of the relationship between experimentally observed spin kinetics (transitions between different environments [Formula: see text]) and corresponding chemical kinetics (transitions between distinct chemical species; e.g., free host and complexed host molecule). The advantages of using analytical solutions for two-, three- or generally N-state exchange lineshapes (without J-coupling) over the widely used numerical calculation for NMR spectral fitting are presented. Several aspects of exchange kinetics including the generalization of coalescence conditions in two-state exchange, the possibility of multiple processes between two states, and differences between equilibrium and steady-state modes are discussed. 'Reduced equivalent schemes' are introduced for spin kinetics containing fast-exchanging states, effectively reducing the number of exchanging states. The theoretical results have been used to analyze a host-guest system containing an oxoporphyrinogen complexed with camphorsulfonic acid and several other literature examples, including isomerization, protein kinetics, or enzymatic reactions. The theoretical treatment and experimental examples present an expansion of the systematic approach to rigorous analyses of systems with rich chemical kinetics through NMR lineshape analysis.

Enantiomeric Excess Dependent Splitting of NMR Signal through Dynamic Chiral Inversion and Coligand Exchange in a Coordination Complex.

Nuclear magnetic resonance (NMR) spectroscopy cannot be used to discriminate enantiomers, and NMR resonances of enantiomeric mixtures are generally not affected by enantiomeric excess (ee). Here, we report that a coordination complex (L·2Zn·3C), where L is a salen-like prochiral ligand and C is an exchangeable acetate coligand, exhibits symmetrical splitting of one of the 1H NMR resonances of L with the degree of splitting linearly proportional to ee of the chiral guest coligand C, 2-phenoxypropionic acid. Despite the well-defined chirality in the crystal structure of L·2Zn·3C, concurrent fast chiral inversion and coligand exchange in solution renders L·2Zn·3C the primary example of prochiral solvating agent (pro-CSA) based on a coordination complex. Notably, the NMR resonances remain split even in dilute solution due to the lack of chiral guest dissociation in the coligand exchange system. This work provides new insights into chiral transfer events in metal-ligand complexes.

Knock-on synthesis of tritopic calix[4]pyrrole host for enhanced anion interactions.

Interactions of anionic guests with a tritopic peripherally functionalized conjugated calix[4]pyrrole host (1) prepared using a regioselective synthetic method is reported. The regioselectivity of synthesis relies on selective N-alkylation of the calix[4]pyrrole caused by peripheral substitution of one pyrrole group with subsequent N-alkylation at the opposing pyrrole group termed by us 'knock-on' regioselectivity. The resulting host molecule exhibits anion interactions with common chloride and nitrate anions enhanced by an order of magnitude over the parent conjugated calix[4]pyrrole. Combined analysis of 1H NMR and UV-vis spectroscopic titration data enabled an evaluation of binding strengths of anions with the host KA in a binding model where the salt dissociation process is also incorporated in the form of its dissociation constant Kd. Anions could be classified as two types based on their interactions with 1: Type A anions (chloride, nitrate, perchlorate, hydrogensulphate) associate as 1 : 1 complexes through hydrogen bonding while interactions involving Type B anions (acetate, fluoride, dihydrogenphosphate) are complicated by host deprotonation and/or countercation association. Hosts based on rim-functionalized calix[4]pyrroles such as 1 represent a promising new family of chromophores for estimation of biologically relevant anions or other species.

Structural Modulation of Chromic Response: Effects of Binding-Site Blocking in a Conjugated Calix[4]pyrrole Chromophore.

Herein, we modulate the chromic response of a highly colored tetrapyrrole macrocycle, namely, tetrakis(3,5-di-tert-butyl-4-oxocyclohexadien-2,5-yl)porphyrinogen (OxP) by structural modification. N-Benzylation at the macrocyclic nitrogen atoms leads to stepwise elimination of the two calix[4]pyrrole-type binding sites of OxP and serial variation of the chromic properties of the products, double N-benzylated Bz2OxP and tetra N-benzylated Bz4OxP. The halochromic (response to acidity) and solvatochromic (response to solvent polarity) properties were studied by using UV/Vis spectroscopy and NMR spectroscopy in nonpolar organic solvents. Titration experiments were used to generate binding isotherms to elucidate their binding properties with difluoroacetic acid. Differences in the halochromic properties of the compounds allowed construction of a colorimetric scale of acidity in nonpolar solvents, as the compounds in the series OxP, Bz2OxP, and Bz4OxP are increasingly difficult to protonate but maintain their propensity to change color upon protonation. The concurrent effects of binding-site blocking and modulation of acidity sensitivity are important new aspects for the development of colorimetric indicators.

Improving the Colloidal Stability of Temperature-Sensitive Poly(N-isopropylacrylamide) Solutions Using Low Molecular Weight Hydrophobic Additives.

Poly(N-isopropylacrylamide) (PNIPAM) is an important polymer with stimuli-responsive properties, making it suitable for various uses. Phase behavior of the temperature-sensitive PNIPAM polymer in the presence of four low-molecular weight additives tert-butylamine (t-BuAM), tert-butyl alcohol (t-BuOH), tert-butyl methyl ether (t-BuME), and tert-butyl methyl ketone (t-BuMK) was studied in water (D2O) using high-resolution nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering. Phase separation was thermodynamically modeled as a two-state process which resulted in a simple curve which can be used for fitting of NMR data and obtaining all important thermodynamic parameters using simple formulas presented in this paper. The model is based on a modified van't Hoff equation. Phase separation temperatures T p and thermodynamic parameters (enthalpy and entropy change) connected with the phase separation of PNIPAM were obtained using this method. It was determined that T p is dependent on additives in the following order: T p(t-BuAM) > T p(t-BuOH) > T p(t-BuME) > T p(t-BuMK). Also, either increasing the additive concentration or increasing pK a of the additive leads to depression of T p. Time-resolved 1H NMR spin-spin relaxation experiments (T 2) performed above the phase separation temperature of PNIPAM revealed high colloidal stability of the phase-separated polymer induced by the additives (relative to the neat PNIPAM/D2O system). Small quantities of selected suitable additives can be used to optimize the properties of PNIPAM preparations including their phase separation temperatures, colloidal stabilities, and morphologies, thus improving the prospects for the application.