bluuebunny/crossref_metadata_2025 huggingface dataset:
Interaction Energy Analysis of Monovalent Inorganic Anions in Bulk Water Versus Air/Water Interface
Authors: Herbert John , Paul Suranjan
Published: February 2022

Soft anions exhibit surface activity at the air/water interface that can be probed using surface-sensitive vibrational spectroscopy, yet the statistical mechanics behind this surface activity remains a matter of debate. Here, we examine the nature of anion--water interactions at the air/water interface using a combination of molecular dynamics simulations and quantum-mechanical energy decomposition analysis based on symmetry-adapted perturbation theory. Results are presented for a set of monovalent anions including Cl–, Br–, I–, CN–, OCN–, SCN–, NO2–, NO3–, and ClOn– (n = 1, 2, 3, 4), several of which are archetypal examples of surface-active ions. In all cases, we find that anion–water interaction energies are systematically larger in bulk water although the difference (with respect to the interaction energy in the interfacial environment) is well within the magnitude of the instantaneous fluctuations. Specifically for the surface-active species Br–(aq), I–(aq), ClO4–(aq), and SCN–(aq), and also for ClO–(aq), the charge-transfer (CT) energy is found to be slightly larger at the interface than it is in bulk water, but in all cases the CT stabilization amounts to < 20% of the total induction energy. CT-free polarization energies are systematically larger in bulk water, for all of the ions. This analysis complements our recent work suggesting that the short-range solvation structure around these ions is scarcely different at the air/water interface from what it is in bulk water. Together, these observations suggest that changes in first-shell hydration structure around soft anions cannot explain observed surface activities.
Cooperative C-O Bond Activation by a Heterobinuclear Al-Fe Complex Operating by a Radical Pair Mechanism
Authors: Sinhababu Soumen , Radzhabov Maxim , Mankad Neal
Published: February 2022

Activation of inert molecules like CO2 is often mediated by cooperative chemistry between two reactive sites within a cata-lytic assembly, the most common form of which is Lewis acid/base bifunctionality observed in both natural metalloenzymes and synthetic systems. Here, we disclose a heterobinuclear complex with an Al-Fe bond that instead activates CO2 and other substrates through cooperative behavior of two radical intermediates. The complex L(Me)Al-Fp (2, L = HC{(CMe)(2,6-iPr2C6H3N)}2, Fp = FeCp(CO)2) was found to insert CO2 and cyclohexene oxide, producing LAl(Me)(µ:κ2-O2C)Fp (3) and LAl(Me)(µ-OC6H10)Fp (4), respectively. Further atom transfer, decarbonylation, and isomerization reactivity was also ob-served. Detailed mechanistic studies on the CO2 and epoxide insertion reactions indicate an unusual mechanism in which (i) the Al-Fe bond dissociates homolytically to generate formally AlII and FeI metalloradicals, then (ii) the metalloradicals add to substrate in a pairwise fashion initiated by O-coordination to Al. The accessibility of this unusual mechanism is aided, in part, by the redox non-innocent nature of L that stabilizes formally AlII intermediates with predominantly AlIII-like character. This “radical pair” pathway represents an unprecedented mechanism for CO2 activation.
Frustrated Lewis Pair Stabilized Phosphoryl Nitride (NPO), a Mono Phosphorus Analogue of Nitrous Oxide (N2O)
Authors: Eckhardt André , Riu Martin-Louis , Müller Peter , Cummins Christopher
Published: February 2022

Phosphoryl nitride (NPO) is a highly reactive intermediate, and its chemistry has only been explored under matrix isolation conditions so far. Here we report the synthesis of an anthracene (A) and phosphoryl azide-based molecule (N3P(O)A) that acts as a molecular synthon of NPO. Experimentally, N3P(O)A dissociates thermally with a first order kinetic half-life that is associated with an activation enthalpy of ΔH⧧ = 27.5 ± 0.3 kcal mol–1 and an activation entropy of ΔS⧧ = 10.6 ± 0.3 cal mol–1 K–1 that are in good agreement with calculated DLPNO-CCSD(T)/cc-pVTZ//PBE0-D3(BJ)/cc-pVTZ energies. In solution N3P(O)A undergoes Staudinger reactivity with tricyclohexylphosphine (PCy3) and subsequent complexation with tris(pentafluorophenyl)borane (B(C6F5)3, BCF) to form Cy3P-NP(A)O-B(C6F5)3. Anthracene is cleaved off photochemically to form the frustrated Lewis pair (FLP) stabilized NPO complex Cy3P⊕-N=P-O-B⊖(C6F5)3. Intrinsic Bond Orbital (IBO) analysis suggests that the adduct is zwitterionic, with a positive and negative charge localized on the complexing Cy3P and BCF, respectively.
Mechanochemical solid state synthesis of a bifunctional copper(I)/N-heterocyclic carbene complex and its catalytic activity in hydrogenative transformations
Authors: Remy-Speckmann Ina , Zimmermann Birte , Gorai Mahadeb , Johannes Teichert , Lerch Martin
Published: February 2022

A sophisticated bifunctional catalyst bearing a copper(I)/N-heterocyclic carbene and a guanidine organocatalyst has been prepared by a mechanochemical synthesis in a ball mill. This approach circumvents commonly employed silver(I) complexes which are associated with significant and undesired waste formation. Due to the bifunctional nature of the desired complex, earlier mechanochemical conditions were not applicable and a new protocol based on cheap and readily available K3PO4 as base has been developed. The resulting complex has been shown to be active in a variety of reduction/hydrogenation transformations employing dihydrogen as terminal reducing agent.
Conductivity mechanism in ionic 2D carbon nitrides: from hydrated ion motion to enhanced photocatalysis
Authors: Kröger Julia , Podjaski Filip , Savaşçı Gökçen , Moudrakovski Igor , Jimenez-Solano Alberto , Terban Maxwell W. , Bette Sebastian , Duppel Viola , Joos Markus , Senocrate Alessandro , Dinnebier Robert , Ochsenfeld Christian , Lotsch Bettina Valeska
Published: February 2022

Carbon nitrides are among the most studied materials for photocatalysis, however, limitations arise from inefficient charge separation and transport within the material. Here, this aspect is addressed in the 2D carbon nitride poly(heptazine imide) (PHI) by investigating the influence of various counterions, such as M = Li+, Na+, K+, Cs+, Ba2+, NH4+ and tetramethyl ammonium, on the material’s conductivity and photocatalytic activity. These ions in the PHI pores affect the stacking of the 2D layers, which further influences the predominantly ionic conductivity in M-PHI. Na-containing PHI outperforms the other M-PHI in various relative humidity (RH) environments (0-42 %RH) in terms of conductivity, likely due to pore channel geometry and size of the (hydrated) ion. With increasing RH, the ionic conductivity increases by 4-5 orders of magnitude (for Na-PHI up to 10-5 S cm-1 at 42 %RH). At the same time, the highest photocatalytic hydrogen evolution rate is observed for Na-PHI, which is mirrored by increased photo-generated charge carrier lifetimes, pointing to efficient charge carrier stabilization by mobile ions. These results indicate that ionic conductivity is an important parameter that can influence the photocatalytic activity. Besides, RH-dependent ionic conductivity is of high interest for separators, membranes, or sensors.
Molecular Design and Synthesis of Dicarbazolophane-Based Cen-trosymmetric through-Space Donors for Solution-Processed TADF OLEDs
Authors: Zhang Zhen , Diesing Stefan , Crovini Ettore , Kumar Gupta Abhishek , Spuling Eduard , Gan Xuemin , Fuhr Olaf , Nieger Martin , Hassan Zahid , Samuel Ifor , Bräse Stefan , Zysman-Colman Eli
Published: February 2022

Conjugation-extended carbazolophane donors, dicarbazolophanes (DCCP), were designed and synthesized by a multi-fold stepwise Pd-catalyzed Buchwald-Hartwig amination/ring cyclization process. Further, elaboration of the DCCP core is possible with introduction of pendant carbazole derivative groups. This provided a way of tuning the optoelectronic properties of the thermally activated delayed fluorescence (TADF) compounds DCCPTRZtBu2, dtBuCzDCCPTRZtBu2, and dMeOCzDCCPTRZtBu2. Solution-processed OLEDs were fabricated and achieved maxi-mum external quantum efficiencies (EQEmax) of 8.2% and EQE of 7.9% at 100 cd/m2.
Nanoplastic transport in aqueous environments: The role of chemo-electric properties and hydrodynamic forces for nanoplastic-mineral interaction.
Authors: Müller Sascha , Fiutowski Jacek , Rubahn Horst-Günter , Posth Nicole Rita
Published: February 2022

The fate and transport characteristics of nanoplastic (NP) through different environmental systems is largely governed by physio-chemical processes and their specific interaction with environmental constituents (i.e., minerals, dissolved species, suspended particles). A hydrodynamic component present in almost all terrestrial and marine aqueous environments impact the physio-chemical processes micron-scale is largely overlooked in NP transport studies. Therefore, we tested the interaction behavior of nanosized plastic polystyrene particles of various coatings in the presence of minerals abundant in the Earth crust within a hydrodynamic continuum representing flow rates from groundwater to surface water systems. Our batch experiments show that particle-mineral adsorption is largely driven by the magnitude of opposite charge configurations, which is either produced by mineral type or specific nanoplastic surface coating. Zetapotential serves as a good predictor of adsorption between uncoated and carboxyl-coated polystyrene with minerals. It fails, however, to predict adsorption behavior between NH2 coated polystyrene and apatite or feldspars, due to the more complex and varying compositions of these minerals. Incorporating the hydrodynamic force component into the particle- mineral interaction scheme reproduces those adsorption trends at slow flowrates of 1e-04 m/d. However, increasing flow rates by a factor of 100 modifies charge-driven adsorption between minerals and plastics. This study highlights the unabating importance of hydrodynamic conditions when predicting nanoplastic transport in different subsurface environments, and has implications for nanoplastic behavior in both terrestrial and marine aqueous environments.
Virtual screening of norbornadiene-based molecular solar thermal energy storage systems using a genetic algorithm
Authors: Ree Nicolai , Koerstz Mads , Mikkelsen Kurt V. , Jensen Jan H.
Published: February 2022

We present a computational methodology for the screening of a chemical space of 10²⁵ substituted norbornadiene molecules for promising kinetically stable molecular solar thermal (MOST) energy storage systems with high energy densities that absorb in the visible part of the solar spectrum. We use semiempirical tight-binding methods to construct a dataset of nearly 34,000 molecules and train graph convolutional networks to predict energy densities, kinetic stability, and absorption spectra and then use the models together with a genetic algorithm to search the chemical space for promising MOST energy storage systems. We identify 15 kinetically stable molecules, five of which have energy densities greater than 0.45 MJ/kg and the main conclusion of this study is that the largest energy density that can be obtained for a single norbornadiene moiety with the substituents considered here, while maintaining a long half-life and absorption in the visible spectrum, is around 0.55 MJ/kg.
Don’t overweight weights: Evaluation of weighting strategies for multi-task bioactivity classification models
Authors: Humbeck Lina , Morawietz Tobias , Sturm Noe , Zalewski Adam , Harnqvist Simon , Heyndrickx Wouter , Holmes Matthew , Beck Bernd
Published: February 2022

Machine learning models predicting the bioactivity of chemical compounds belong nowadays to the standard tools of cheminformaticians and computational medicinal chemists. Multi-task and federated learning are promising machine learning approaches that allow priva-cy-preserving usage of large amount of data from diverse sources, which is crucial for achieving good generalization and high-performance results. Using large, real world data sets from six pharmaceutical companies, here we investigate different strategies for averaging weighted task loss functions to train multi-task bioactivity classification models. The weighting strategies shall be suitable for federated learning and ensure that learning efforts are well distributed even if data are diverse. Comparing several approaches using weights that depend on the number of sub-tasks per assay, task size, and class balance, respectively, we find that a simple sub-task weighting approach leads to robust model performance for all investigated data sets and is especially suited for federated learning.
Artificial Intelligence-Enhanced Quantum Chemical Method with Broad Applicability
Authors: Zheng Peikun , Zubatyuk Roman , Wu Wei , Isayev Olexandr , Dral Pavlo O.
Published: February 2022

High-level quantum mechanical (QM) calculations are indispensable for accurate explanation of natural phenomena on the atomistic level. Their staggering computational cost, however, poses great limitations, which luckily can be lifted to a great extent by exploiting advances in artificial intelligence (AI). Here we introduce the general-purpose, highly transferable artificial intelligence–quantum mechanical method 1 (AIQM1). It approaches the accuracy of the ‘gold-standard’ coupled cluster QM method with low computational speed of the approximate low-level semiempirical QM methods. AIQM1 can provide accurate ground-state energies for diverse organic compounds as well as geometries for even challenging systems such as large conjugated compounds (fullerene C60) close to experiment. Noteworthy, our method’s accuracy is also good for ions and excited-state properties, although the neural network part of AIQM1 was never fitted to these properties.
Dynamic Amide Formation by Reversible Nitrone Exchange of Potassium Acyltrifluoroborates (KATs) and Hydroxylamines in Aqueous Conditions
Authors: Dzeng Yi-Chung , Bode Jeffrey
Published: February 2022

The condensation of potassium acyltrifluoroborates (KATs) and hydroxylamines occurs under ambient, aqueous conditions to form KAT nitrones in a reversible manner. The KAT nitrones exchange rapidly under aqueous acidic conditions, resulting in a dynamic covalent library that can be converted to the corresponding static amides by treatment with strong acid. Extensive studies on the conditions and kinetics show that – counterintuitively – KAT nitrone formation is accelerated by water. The overall process serves as a dynamic system operating at room temperature under aqueous conditions with the rare ability of trapping the mixture into stable secondary amides.
Compacting the density matrix in quantum dynamics: Singular value decomposition of the surprisal and the dominant constraints for anharmonic systems
Authors: Komarova Ksenia , Remacle Francoise , Levine Raphael D.
Published: February 2022

We introduce a practical method for compacting the time evolution of the quantum state of a closed physical system. The density matrix is specified as a function of a few time-independent observables where their coefficients are time-dependent. The key mathematical step is the vectorization of the surprisal, the logarithm of the density matrix, at each time point of interest. The time span used depends on the required spectral resolution. The entire course of the system evolution is represented as a matrix where each column is the vectorized surprisal at the given time point. Using singular value decomposition, SVD, of this matrix we generate realistic approximations for the time-independent observables and their respective time dependent coefficients. This allows a simplification of the algebraic procedure for determining the dominant constraints (the time-independent observables) in the sense of the maximal entropy approach. A nonstationary coherent initial state of a Morse oscillator is used to introduce the approach. We derive analytical exact expression for the surprisal as a function of time and this offers a benchmark for comparison with the accurate but approximate SVD results. We discuss two examples of a Morse potential of different anharmonicities, the H2 and I2 molecules. We further demonstrate the approach for a two coupled electronic states problem, the well studied non radiative decay of pyrazine from its bright state. Five constraints are found to be enough to capture the ultrafast electronic population exchange and to recover the dynamics of the wave packet in both electronic states.
Enantioselective synthesis of atropisomeric indoles via iron catalysed oxidative cross-coupling
Authors: Surgenor Richard , Liu Xiangqian , Myers William , Smith Martin
Published: February 2022

Heterobiaryl compounds that exhibit axial chirality are of increasing value and interest across several fields, but direct oxidative methods for their enantioselective synthesis are elusive. Here we disclose that an iron catalyst in the presence of a chiral PyBOX ligand and an oxidant enables direct coupling between naphthols and indoles to yield atropisomeric heterobiaryl compounds with high levels of enantioselectivity. The reaction exhibits remarkable chemoselectivity and exclusively yields cross-coupled products without competing homocoupling. Mechanistic investigations enable us to postulate that the reaction proceeds through selective formation of an indole radical which is trapped by a chiral iron naphthoate in a radical–anion type coupling process. We envision that this simple, cheap, and sustainable catalytic manifold will facilitate access to a range of heterobiaryl compounds and enable their applications across the fields of materials science, medicinal chemistry, and catalysis.
Template-Directed Synthesis of Bivalent, Broad-Spectrum Hosts for Neuromuscular Blocking Agents
Authors: Selinger Allison J. , Cavallin Natalie A. , Hof Fraser
Published: February 2022

We report on the synthesis of bivalent water soluble calix[4]arene and calix[5]arene hosts, Super-sCx4 and Super-sCx5 as new broad-spectrum supramolecular binders of neuromuscular blocking agents (NMBAs). Synthesis was achieved using the target bisquaternary amine NMBAs as a template to link two highly anionic p-sulfonatocalixarene building blocks in aqueous solution. Bivalent anionic hosts Super-sCx4 and Super-sCx5 bind by engaging both quaternary amines present on a variety of NMBAs. We report low μM binding to structurally diverse alkyl, steroidal, curarine and benzylisoquinoline NMBAs with high selectivity over the neurotransmitter acetylcholine.
Modular Terpene Synthesis Enabled by Mild Electrocatalytic Couplings
Authors: Harwood Stephen , Palkowitz Maximilian , Gannett Cara , Perez Paulo , Yao Zhen , Sun Lijie , Abruña Hector , Anderson Scott , baran phil
Published: February 2022

The synthesis of terpenes is a large field of research that is woven deeply into the history of chemistry. Terpene biosynthesis is a case-study of how the logic of a modular design can lead to diverse structures with unparalleled efficiency. This work mimics Nature by leveraging modern Ni-catalyzed electrochemical sp2–sp3 decarboxylative coupling reactions—enabled by Ag-nanoparticle modified electrodes—to intuitively assemble terpene natural products and complex polyenes. The step-change in efficiency of this approach is exemplified through the scalable preparation of 13 complex terpenes, which minimized protecting group manipulations, functional group interconversions, and redox fluctuations. Finally, the mechanistic aspects of the essential functionalized electrodes are studied in depth through a variety of spectroscopic and analytical techniques.
Optimal Representation of the Nuclear Ensemble: Application to Electronic Spectroscopy
Authors: Sršeň Štěpán , Slavíček Petr
Published: February 2022

Nuclear densities are frequently represented by an ensemble of nuclear configurations or points in the phase space in various contexts of molecular simulations. The size of the ensemble directly affects the accuracy and computational cost of subsequent calculations of observable quantities. In the present work, we address the question of how many configurations do we need and how to select them most efficiently. We focus on the nuclear ensemble method in the context of electronic spectroscopy, where thousands of sampled configurations are usually needed for sufficiently converged spectra. The proposed representative sampling technique allows for a dramatic reduction of the sample size. By using an exploratory method, we model the density from a large sample in the space of transition properties. The representative subset of nuclear configurations is optimized by minimizing its Kullback-Leibler divergence to the full density with simulated annealing. High-level calculations are then performed only for the selected subset of configurations. We tested the algorithm on electronic absorption spectra of three molecules: (E)-azobenzene, the simplest Criegee intermediate, and hydrated nitrate anion. Typically, dozens of nuclear configurations provided sufficiently accurate spectra. A strongly forbidden transition of the nitrate anion presented the most challenging case due to rare geometries with disproportionately high transition intensities. This problematic case was easily diagnosed within the present approach. We also discuss various exploratory methods and a possible extension to dynamical simulations.
Perplexity-based molecule ranking and bias estimation of chemical language models
Authors: Moret Michael , Grisoni Francesca , Katzberger Paul , Schneider Gisbert
Published: February 2022

Chemical language models (CLMs) can be employed to design molecules with desired properties. CLMs generate new chemical structures in the form of textual representations, such as the simplified molecular input line entry systems (SMILES) strings, in a rule-free manner. However, the quality of these de novo generated molecules is difficult to assess a priori. In this study, we apply the perplexity metric to determine the degree to which the molecules generated by a CLM match the desired design objectives. This model-intrinsic score allows identifying and ranking the most promising molecular designs based on the probabilities learned by the CLM. Using perplexity to compare “greedy” (beam search) with “explorative” (multinomial sampling) methods for SMILES generation, certain advantages of multinomial sampling become apparent. Additionally, perplexity scoring is performed to identify undesired model biases introduced during model training and allows the development of a new ranking system to remove those undesired biases.
Electrochemical Nitric Oxide Reduction on Metal Surfaces
Authors: Wan Hao , Bagger Alexander , Rossmeisl Jan
Published: February 2022

Electrocatalytic denitrification is a promising technology for removing NOx species (NO3− , NO2− and NO). For NOx electroreduction (NOxRR), there is a desire for understanding the catalytic parameters that control the product distribution. Here, we elucidate selectivity and activity of catalyst for NOxRR. At low potential we classify metals by the binding of ∗NO versus ∗H. Analogous to classifying CO2 reduction by ∗CO vs ∗H, Cu is able to bind ∗NO while not binding ∗H giving rise to a selective NH3 formation. Besides being selective, Cu is active for the reaction found by an activity-volcano. For metals that does not bind NO the reaction stops at NO, similar to CO2-to-CO. At potential above 0.3 V vs RHE, we speculate a low barrier for N coupling with NO causing N2O formation. The work provide a clear strategy for selectivity and aims to inspire future research on NOxRR.
A Diastereodivergent and Enantioselective Approach to syn- and anti-Diamines: Development of 2-Azatrienes for Cu-Catalyzed Reductive Couplings with Imines that Furnish Allylic Amines
Authors: Zhou Pengfei , Shao Xinxin , Malcolmson Steven
Published: February 2022

We introduce a new reagent class, 2-azatrienes, as a platform for catalytic enantioselective synthesis of allylic amines. Herein, we demonstrate their promise by diasteredivergent and enantioselective synthesis of syn- and anti-1,2-diamines by Cu-bis(phosphine)-catalyzed reductive couplings with imines. With Ph-BPE, anti-diamines are obtained, and with the rarely utilized t-Bu-BDPP, syn-diamines are generated.
Taming Phosphorus Mononitride (PN)
Authors: Eckhardt Andre , Riu Martin-Louis , Ye Mengshan , Mueller Peter , Bistoni Giovanni , Cummins Christopher
Published: February 2022

Phosphorus mononitride (PN) only has a fleeting existence on Earth and molecular precursors for a mild release of the molecule to enable chemical synthesis in solution do not exist. Here we report the synthesis of an anthracene (A) based molecular precursor (N3PA) that dissociates into dinitrogen (N2), A and PN in solution with a first order half-life of roughly t 1/2 = 30 min at room temperature associated with an activation enthalpy of ΔH ⧧ = 19.5 ± 1.7 kcal mol –1 and an activation entropy of ΔS ⧧ = −8.8 ± 0.8 cal mol –1 K –1 . Heated under vacuum N3PA decomposes in an explosive fashion at around 42 °C as demonstrated in a molecular beam mass spectrometry (MBMS) study. N3PA serves as a PN transfer reagent as demonstrated in the synthesis of [(dppe)Fe(Cp*)(NP)][BArF24]. Surprisingly, the terminal N-bonded linkage isomer is energetically preferred due to significant covalent iron pnictogen bond character and associated less unfavorable Pauli repulsion in the metal-ligand interaction.
Exploring Isovalent Substitution of Lead with Nickel in Methylammonium Lead Iodide Perovskites
Authors: Smith Emily , Javaid Hamza , Abdullah Muhammad , Kittilstved Kevin , Venkataraman D.
Published: February 2022

We replaced lead ions with nickel ions in methylammonium lead triiodide (MAPbI3) perovskites and studied their electronic and photophysical properties. We synthesized thin films using solutions containing methylammonium iodide (MAI), PbI2, and NiI2 with varying Pb/Ni precursor ratios. We show that MAPbI3 retains its three-dimensional perovskite structure in the presence of Ni2+. We were able to incorporate up to 30% Ni2+ before we note the appearance of unconverted NiI2 via X-ray diffraction. Although the structures of NiI2 and PbI2 are isostructural and the metal ions have the same oxidation states, the bulk material did not behave as a solid solution. Furthermore, the addition of Ni2+ thoroughly quenched the emission of MAPbI3, suggesting that Ni2+ may act as a recombination center for excited charge carriers. Additionally, the materials displayed significant instability towards water. Thus, we conclude that there is a limited application for nickel and perhaps other transition metal ions as a replacement ion for lead in thin-film perovskite photovoltaic devices fabricated in these conditions.
WARNA LOKAL JAWA NOVEL PASAR KARYA KUNTOWIJOYO DAN SUMBANGSIHNYA TERHADAP PENGEMBANGAN KARAKTER PESERTA DIDIK
Authors: Rahaya Ivana Septia , Subiyantoro Slamet , Setiawan Budhi
Published: February 2022

The purpose of this research is to describe and explain Javanese local color in Pasar novel by Kuntowijoyo and its contribution to the character development of students. This research is descriptive qualitative with a literary anthropology approach. Data collection techniques using note-taking techniques, while data analysis techniques are content analysis techniques. The results of this research indicate that Pasar novel contains Javanese local colors such as (a) the setting in Gemolong District; (b) a religious system that believes in the existence of God but still maintains their religious culture; (c) social systems and social organizations that describe the social status of Javanese people; (d) the knowledge system of Javanese priyayi figures; (e) language; and (f) Javanese philosophy which is used as a principle of society's life. The local color in Pasar novel has an important role to add to cultural knowledge and positive values, so if that novel is used as literary teaching materials it will help students develop their characters for the better.Tujuan penelitian ini adalah mendeskripsikan warna lokal Jawa novel Pasar karya Kuntowijoyo serta sumbangsihnya terhadap pengembangan karakter peserta didik. Penelitian ini merupakan penelitian deskriptif kualitatif dengan pendekatan antropologi sastra. Teknik pengumpulan data menggunakan teknik baca catat, sedangkan teknik analisis data ialah teknik analisis isi (content analysis). Hasil penelitian ini menunjukkan bahwa novel Pasar mengandung warna lokal Jawa seperti (a) latar tempat di Kecamatan Gemolong; (b) sistem religi yang mempercayai adanya Tuhan, tetapi tetap mempertahankan budaya religinya; (c) sistem kemasyarakatan dan organisasi sosial yang menggambarkan status sosial masyarakat Jawa; (d) sistem pengetahuan tokoh priyayi Jawa; (e) bahasa; serta (f) falsafah Jawa yang digunakan sebagai prinsip hidup masyarakat. Warna lokal dalam novel Pasar memiliki peran penting untuk menambah pengetahuan budaya dan nilai-nilai positif sehingga apabila novel tersebut digunakan sebagai bahan ajar sastra, akan membantu peserta didik mengembangkan karakternya menjadi lebih baik.
IDENTITAS BUDAYA TIMOR DALAM ANTOLOGI CERPEN MENYUDAHI KABAIR KARYA SAYYIDATI HAJAR: KAJIAN STILISTIKA KULTURAL
Authors: Rejo Uman , Rohmah Nurul Baiti
Published: February 2022

This paper aims to explore and describe the Timor cultural identity contained in Sayyidati Hajar’s anthology of the short stories, Menyudahi Kabair. This Timor cultural identity is more focused on the use of cultural diction and rhetoric tools contained in the short stories by Sayyidati Hajar. To explore and develop this mission, the literary approach used is a cultural stylistic approach. There are 12 short stories in this anthology, but only 5 short stories are used as the object of study. The method used is a qualitative descriptive method. The results and discussion show that the cultural diction which is used as a marker of Timor cultural identity can be categorized into a cultural one which indicates a nickname or designation, place names, local traditions, commands, actions, sounds or special sounds, names of animals, and designations for a house name. This cultural diction has a cultural meaning related to Timor culture according to Sayyidati Hajar’s expression through the short stories she produces.The means of rhetoric as a support for this cultural diction can be seen from various aspects, including in terms of sentence structure, the technique of expression used, the accuracy or appropriateness of the choice of words used, the meaning of the word, the lexical structure, changes in meaning, and whether or not the meaning represented in the short story.Tulisan ini bertujuan untuk mengeksplorasi dan mendeskripsikan identitas budaya Timor yang terdapat dalam antologi cerpen Menyudahi Kabair karya Sayyidati Hajar. Identitas budaya Timor tersebut lebih difokuskan pada penggunaan diksi-diksi kultural dan sarana retorika yang terkandung dalam cerpen karya Sayyidati Hajar. Untuk mengeksplorasi dan mengembangkan misi tersebut, maka pendekatan sastra yang digunakan adalah pendekatan stilistika kultural. Ada 12 cerpen yang terdapat dalam antologi ini, tetapi hanya 5 cerpen yang dijadikan sebagai objek kajian. Metode yang digunakan adalah metode deskriptif kualitatif. Hasil dan bahasan menunjukkan diksi-diksi kultural yang digunakan sebagai penanda identitas budaya Timor dapat dikategorikan menjadi diksi kultural yang menunjukkan panggilan atau sebutan, nama tempat, tradisi lokal setempat, perintah, tindakan, suara atau bunyi-bunyi khusus, nama binatang, dan sebutan untuk nama rumah. Diksi kultural tersebut memiliki makna kultural yang berkaitan dengan kebudayaan Timor sesuai ekspresiSayyidati Hajar melalui cerpen-cerpen yang dihasilkannya. Sarana retorika sebagai pendukung diksi-diksi kultural tersebut dapat dilihat dari berbagai segi, di antaranya segi struktur kalimat, teknik pengungkapan yang digunakan, ketepatan atau kesesuaian pilihan kata yang digunakan, makna kata, struktur leksikal, perubahan makna, dan langsung ti-daknya makna yang direpresentasikan dalam cerpen.
EKSPLORASI FOLKLOR KAMPUNG PITU NGLANGGERAN (KAJIAN SASTRA DENGAN PENDEKATAN PARIWISATA)
Authors: Utami Dyah Ayu Putri , Kusmiatun Ari
Published: February 2022

This study includes a qualitative descriptive study that aims to explore the folklore of Kampung Pitu using a tourism literature approach. This approach focuses on the study of the phenomena of literary works, writers, literary festivals, and folklore that make a real contribution to the development of tourism. The data of this research are in the form of sentences in the folklore that developed in Pitu Village. Data collection techniques using interviews and documentation. Data analysis techniques, namely reduction, presentation, and dra-wing conclusions. The results showed that (1) the folklore in Kampung Pitu consists of the legend of the origin of Kampung Pitu, the myth of Telaga Guyangan, and the myth of Rasulan; (2) each story has an appeal in rules/laws, stories, and rituals; (3) developing folklore has the potential to become a tourist area branding. This branding needs to be supported by the metamorphosis of folklore into theatrical performances, ballet, short films, folklore books, or other narrative forms that can be used as promotions.Penelitian ini termasuk penelitian deskriptif kualitatif yang bertujuan untuk mengeksplorasi cerita rakyat Kampung Pitu menggunakan pendekatan sastra pariwisata. Pendekatan ini memfokuskan kajian pada fenomena karya sastra, sastrawan, festival sastra, dan cerita rakyat yang memberikan sumbangan nyata dalam perkembangan kepariwisataan. Data penelitian ini berupa kalimat dalam cerita rakyat yang berkembang di Kampung Pitu. Teknik pengumpulan data menggunakan wawancara dan dokumentasi. Teknik analisis data, yaitu reduksi, penyajian, dan penarikan simpulan. Hasil penelitian menunjukkan bahwa (1) cerita rakyat di Kampung Pitu terdiri atas Legenda asal-usul Kampung Pitu, mite Telaga Guyangan, dan mite Rasulan; (2) masing-masing cerita memiliki daya tarik dalam aturan/hukum, cerita, dan ritual; (3) cerita rakyat yang berkembang berpotensi untuk menjadi branding kawasan wisata. Branding ini perlu didukung oleh metamorfosis cerita rakyat menjadi pertunjukkan teater, sendratari, film pendek, buku cerita rakyat, atau bentuk narasi lain yang dapat digunakan sebagai promosi.
LEKSIKON EKOAGRARIS DALAM BUDAYA PERTANIAN MASYARAKAT KECAMATAN SUMUR KABUPATEN PANDEGLANG
Authors: Rosidin Odien , Muhyidin Asep
Published: February 2022

The purpose of this study is to explain (1) the lexicon of the process of cultivating rice fields; (2) the process lexicon after harvesting rice; and (3) the lexicon of agricultural tools within the scope of agricultural culture in the Sumur sub-district community, Pandeglang district. This article is derived from the results of research with a descriptive qualitative approach using an ethnographic method based on ecolinguistic theory. Data were obtained from the results of participant observations and interviews with informants as many as 23 people who live in seven villages. The findings of this study are as follows: (1) the lexicon of the process of cultivating rice fields in the form of monomorphemic words; affixed polymorphemic words involving prefixes and confixes and reduplication results; and a combination of two words; (2) the process lexicon after harvesting rice in the form of affixed polymorphemic words involving prefixes and confixes; and a combination of two words; and (3) the lexicon of agricultural tools in the form of monomorphemic words; affixed polymorphemic words involving suffixes; and a combination of two words.Penelitian ini betujuan menjelaskan (1) leksikon proses penggarapan sawah; (2) leksikon proses setelah memanen padi; dan (3) leksikon alat-alat pertanian dalam lingkup budaya pertanian di lingkungan masyarakat Kecamatan Sumur, Kabupaten Pandeglang. Artikel ini berasal dari hasil penelitian dengan pendekatan kualitatif deskriptif berdasarkan ancangan metode etnografis yang berbasis pada teori ekolinguistik. Data diperoleh dari hasil observasi partisipan dan wawancara kepada informan sebanyak 23 orang yang berdomisili di tujuh desa. Penelitian ini menghasilkan tiga temuan. Pertama, leksikon proses penggarapan sawah berupa kata monomorfemis; kata polimorfemis hasil afiksasi yang melibatkan prefiks dan konfiks atau reduplikasi; serta gabungan dua kata. Ketiga, leksikon proses setelah memanen padi berupa kata polimorfemis hasil afiksasi yang melibatkan prefiks dan konfiks serta gabungan dua kata. Ketiga, leksikon alat-alat pertanian berupa kata monomorfemis; kata polimorfemis hasil afiksasi yang melibatkan sufiks dan gabungan dua kata.
Calibration of a New Concrete Damage Plasticity Theoretical Model Based on Experimental Parameters
Authors: Al-Zuhairi Alaa H. , Al-Ahmed Ali H. , Abdulhameed Ali A. , Hanoon Ammar N.
Published: February 2022

The introduction of concrete damage plasticity material models has significantly improved the accuracy with which the concrete structural elements can be predicted in terms of their structural response. Research into this method's accuracy in analyzing complex concrete forms has been limited. A damage model combined with a plasticity model, based on continuum damage mechanics, is recommended for effectively predicting and simulating concrete behaviour. The damage parameters, such as compressive and tensile damages, can be defined to simulate concrete behavior in a damaged-plasticity model accurately. This research aims to propose an analytical model for assessing concrete compressive damage based on stiffness deterioration. The proposed method can determine the damage variables at the start of the loading process, and this variable continues to increase as the load progresses until complete failure. The results obtained using this method were assessed through previous studies, whereas three case studies for concrete specimens and reinforced concrete structural elements (columns and gable beams) were considered. Additionally, finite element models were also developed and verified. The results revealed good agreement in each case. Furthermore, the results show that the proposed method outperforms other methods in terms of damage prediction, particularly when damage is calculated using the stress ratio. Doi: 10.28991/CEJ-2022-08-02-03 Full Text: PDF
Factors Affecting SMEs' Intention to Adopt a Mobile Travel Application based on the Unified Theory of Acceptance and Use of Technology (UTAUT-2)
Authors: Yawised Kritcha , Apasrawirote Darlin , Chatrangsan Maneerut , Muneesawang Paisarn
Published: February 2022

This study is part of a government research project which aims to synthesise the current evidence on the factors affecting the intention of mobile application adoption called ‘Tripper Notifier Application’ (TNA) for the hospitality and tourism industrial sector in Thailand. The focus is on small and medium enterprises (SMEs), which emphasize restaurants, hotels, and attraction sites. The present article examines various factors influencing the intention to use such applications by employing the Unified Theory of Acceptance and Use of Technology 2 (UTAUT-2) as the theoretical underpinning of this research paradigm. Using 84 selected research papers in Scopus published between 2020 and 2022, A thematic analysis incorporating a grounded theory approach to systematically generate themes was conducted, and the findings found three main themes, including business transformation capabilities (BTC), digital transformation capabilities (DTC), and personal innovativeness (PI), as an extension of UTAUT-2 as mediator and moderator variables. To this end, the study fills the research gaps and extends the UTAUT-2 framework by including an initiative of twelve inside attributes-based lines, including performance expectancy, effort expectancy, social influence, facilitating conditions, hedonic motivation, price value, habit behavior, behavioral intention, and use behavior, together with three moderators: age, gender, and experience. Finally, the context dimensions of the UTAUT-2 extensions were mapped to highlight all the constructs of the TNA adoption framework for future research directions. The novel contribution of this study is to fill the gap with both theoretical and practical knowledge. On the theoretical level, this study constitutes constructs based on UTAUT-2 theory as a research-based setting to fill a gap in research. On the practical level, it provides insights and information about new capabilities that SME owners, managers, and practitioners should consider in order to differentiate their own capabilities. Doi: 10.28991/esj-2021-SP1-014 Full Text: PDF
A systematic approach to the economics of regional healthcare
Authors: Serebryakova Tatyana , Gayfullin Airat
Published: February 2022

Healthcare is one of the branches of the Russian economy. The industry is developing on the terms of commercialization, on the one hand, on the other - it has a pronounced social character. The institutional foundations of the healthcare economy are not fully defined, since the industry has been developing in market conditions over the past 30 years. Fragmentary economic processes and indicators have been studied, but a comprehensive description of the health economics model and an assessment of its functioning has not been formed. A systematic approach can be used for these purposes. As a result of the study, a set of components of the health care economy system at the regional level is proposed that meets the goal of evaluating the effectiveness of health care at the regional level.
FEATURES OF TRAINING AND DEVELOPMENT OF STAFF IN THE SPHERE OF THE HOTEL BUSINESS
Authors: Zelenov Vladimir , Erokhin Sergey , Galstyan Vladislav
Published: February 2022

The relevance of the chosen topic is confirmed by the high influence of the success of the training and development system on the effectiveness of personnel management processes and business performance in general, the learning process at the enterprise, in addition to its direct purpose - familiarizing the employee with the company's activities, mastering new knowledge and skills, professional development, is precisely the adaptation period that will allow the employee to further socialize in the team and function successfully
DIRECTIONS OF DIGITALIZATION OF THE AGRO-INDUSTRIAL COMPLEX IN THE CONTEXT OF HUMAN DEVELOPMENT CAPITAL OF RURAL TERRITORIES OF THE RUSSIAN FEDERATION
Authors: Taranova Irina , Syrovatskaya Valentina , Chernov Iliya
Published: February 2022

the article presents the growth dynamics of the gross domestic product of the Rus-sian Federation, the branches of the agro-industrial complex of the Russian Federa-tion for the period 2016-2020, a comparative analysis of growth rates is carried out. The outstripping pace of development of the agro-industrial complex has been es-tablished in comparison with other sectors of the Russian economy. The directions for adjusting the legal documents of the Russian Federation regulating the digitali-zation of agricultural activities are substantiated in the context of the development of human capital in rural areas, strengthening the investment attractiveness and competitiveness of the agro-industrial complex. The results of the study can be used by state authorities of the Russian Federation and subjects of the Russian Fed-eration in the preparation of programs for sectoral and territorial development.
ORGANIZATIONAL AND ECONOMIC ASPECTS OF PROCUREMENT ACTIVITIES TAKING INTO ACCOUNT DIGITAL TRANSFORMATIONS IN THE RUSSIAN FEDERATION
Authors: Alexandrova Margarita , Maslyukova Ekaterina , Simonov Sergei , Yutkina Olga
Published: February 2022

The key purpose of the article is to consider the specifics of public procurement in Russia and abroad, as well as in the regional aspect. The article analyzes the dynamics of customer registration in the Unified Information System, evaluates the effectiveness of procurement activities in various regions of the Russian Federation and sectors of the economy. On this basis, the main factors affecting the effectiveness of public procurement were identified.
THE ROLE OF THE CHEMICAL INDUSTRY IN ENSURING FOOD SECURITY
Authors: Buravova Alena
Published: February 2022

The article is devoted to the role of the chemical industry in ensuring food security. The objectives of ensuring the food security of the state are defined, and the need to activate the internal resources and potential of the state to ensure the food security of the state is justified. The connection of the chemical industry with agriculture and their impact on food security is shown. The statistics of the main indicators of the production of mineral fertilizers and indicators of self-sufficiency are presented, which confirm the importance of the chemical industry and agriculture in ensuring food security.
Self-concept dan Family Support dengan Academic Burnout pada Siswa di Masa Pandemi
Authors: Diyanti Puput Rista
Published: February 2022

Tujuan penelitian adalah untuk mengetahui hubungan antara self-concept dan family support dengan academic burnout pada siswa MI Darussalam di masa pandemic secara parsial dan simultan. Penelitian ini merupakan penelitian kuantitatif korelasional. Subjek pada penelitian ini adalah siswa-MI Darussalam. Jumlah sampel dalam penelitian ini sebanyak 72 siswa kelas dari 266 siswa MI Darussalam dengan teknik probability sampling. Dari populasi tersebu ditetapkan sebanyak 72 siswa dari kelas 4,5,6. Dari hasil penelitian diketahui bahwa self-concept secara signifikan berhubungan negative dengan academic burnout. Kedua, Family support secara signifikan berhubungan negative dengan academic burnout. Ketiga, self-concept dan family support secara signifikan berhubungan negative dengan academic burnout.
Development and Psychometric Properties of MKDP Day’s Instrument as the Measurement of Personality Based on Worker in Kalimantan Selatan
Authors: Hidayatullah M.Syarif , Thaibah Hayatun
Published: February 2022

The personality of a worker or employee is one of the important things to know. However, the development of personality measurement tools made directly in Indonesia is still relatively small. This study aims to develop and identify the psychometric properties of the MKDP Day's Instrument as a personality measurement tool in the context of the workforce in South Kalimantan. The research subjects were 1,123 people between the age of 20-30 years. MKDP Day's Instrument was made by researchers consisting of motivation, cooperation, discipline, and leadership dimensions by taking into account the personality theory of Needs from Murray and Papi Kostick from Kostick. The reliability test used a composite score with a stratified alpha coefficient. The validity test used was confirmatory factor analysis (CFA). The result of the reliability test is 0.832. The four dimensions of the instrument were able to explain 22% of the variables. It found 19 factors that can be formed on the instrument. There are 21 valid items from the initial 60 items with an uneven distribution between the dimensions. Further instrument development is needed to produce better psychometric properties.