bluuebunny/crossref_metadata_2025 huggingface dataset:
Resolving the hydride transfer pathway in oxidative conversion of proline to pyrrole
Authors: Acharya Atanu , Yi Dongqi , Pavlova Anna , Agarwal Vinayak , Gumbart James
Published: February 2022

Thiotemplated pyrrole is a prevailing intermediate in the synthesis of numerous natural products where the pyrrole is tethered to a carrier protein (CP). Biosynthesis of the pyrrole requires oxidation of an L-proline side chain. Herein, we investigated the biocatalytic mechanism of proline-to-pyrrole synthesis using the recently reported (Thapa et al., Biochemistry, 2019, 58, 918) structure of a Type II non-ribosomal protein synthetase (NRPS) Bmp3-Bmp1 (Oxidase-CP) complex. The substrate (L-proline side chain) is attached to the Bmp1(CP) and the catalytic site is located inside the flavin-dependent oxidase (Bmp3). Interestingly, the FAD molecule is free (unbound) within the Bmp3 catalytic site. We show that the FAD isoalloxazine ring is stabilized in the catalytic site of Bmp3 by strong hydrogen bonding with Asn123, Ile125, Ser126, and Thr158. The stability of the dimeric Bmp3 system including one FAD molecule in our simulation suggests that the tetrameric Bmp3 assembly, as found in the crystal structure, is not functionally important. After the initial deprotonation followed by an enamine-imine tautomerization, oxidation of either the C2-C3 bond or the C2-N1 bond, through a hydride transfer (either from C3 or N1), is required for the pyrrole synthesis. Using molecular dynamics simulations, quantum mechanics/molecular mechanics simulations, and electronic structure calculations, we conclude that the hydride transfer is more likely to occur from C3 than N1. Additionally, we demonstrated the elasticity in the oxidase active site through enzymatic synthesis of proline derivatives.
Highly Selective Anion Recognition, Extraction and Deep Removal Using a Superphane
Authors: Zhou Wei , Li Aimin , He Qing
Published: February 2022

Highly selective anion recognition and extraction are critical and challenging to deep removal of pollutants from the environment and effective recovery of valuable chemicals from low–content (at sub–ppm or ppb level) sources. Herein, we detail the gram–scale synthesis of a superphane 2, a new supramolecular host that was found capable of encapsulating ReO4– with high selectivity, as suggested by the single–crystal structures, NMR spectroscopy and theoretical calculations. Under solid–liquid extraction condidtions, 2 proved able to extract perrhenate from the solid mixture containing trace ReO4– (as low as 200 ppb) with near 100% selectivity over other 7 competing anions. Under liquid–liquid extraction conditions, using 2 as the supramolecular extractant, over 99.99% of ReO4– could be separated from the complex simulated aqueous waste streams containing ppm–level perrhenate and large excess of competing ions. Notably, after extraction, 2 could be recycled and reused by simple treatment with NaHCO3. This study opens up the door to development of superphane–based advanced materials for deep elimination of pollutants from the envirenment and purification of chemicals of interest with high efficiency and selectivity.
Electrostatics drive oligomerization and aggregation of human Interferon alpha-2a
Authors: Pohl Christin , Polimeni Marco , Indrakumar Sowmya , Streicher Werner , Peters Guenther , Noergaard Allan , Lund Mikael , Harris Pernille
Published: February 2022

Aggregation and oligomer formation are critical parameters in the field of protein therapeutics and can lead to loss of drug function or even immunogenic responses in patients. Currently two approaches are used to reduce aggregation: (1) finding a suitable formulation which is labor-intensive and requires large protein quantities or (2) engineering the protein by specific, stabilizing mutations, which requires specific knowledge about the protein aggregation pathway. We present a biophysical characterization of the oligomerization and aggregation process by Interferon alpha-2a, a protein drug with antiviral and immunomodulatory properties. We combine high throughput screening with detailed investigations by small-angle X-ray scattering and analytical ultracentrifugation. To get more insight into the molecular mechanism that drives oligomerization and aggregation, we apply molecular Metropolis Monte Carlo simulations. IFNα-2a forms soluble oligomers, which show a fast pH and concentration-dependent equilibrium. We show that attraction between monomers is mainly driven by molecular dipole-dipole interactions, which becomes more pronounced with increasing pH. Repulsion is dominated by ion-ion interaction leading to the formation of insoluble aggregates around the pI which could be prevented by the addition of salt. This study shows how a combination of several methods can help to understand the formation of aggregates and oligomers more systematically and comprehensively, which can lead to better strategies for avoiding aggregation.
Mechanistic Insights into the Rhodium-Catalyzed Aryl C–H Carboxylation
Authors: Liu Deguang
Published: February 2022

The recently reported Rh(II)-catalyzed direct C-H bond activation and lactonization of 2-arylphenols uncovers an attractive strategy to prepare coumarin derivatives with high site-selectivity. Motivated by the mechanistic ambiguity (on the origin of the site-selectivity and the details for lactonization etc.), we conducted a detailed mechanistic study of the rhodium-catalyzed lactonization of 2-arylphenols with density functional theory (DFT) calculations. The results suggest that the reaction occurs via the coordination exchange, C-H bond activation, carboxylation, protonation and lactonization steps. The rate-determining step is the carboxylation step, in which CO2 favorably inserts into the Rh-C bond (instead of the more nucleophilic Rh-O bond). The protonation step after carboxylation is critical, which makes the subsequent CO2-assisted lactonization feasible. Interestingly, the corresponding pKa value of the base can reasonably predict the reaction energy barrier of the C-H bond activation step. The calculations will provide insights and suggestions for the development and advancement of the subsequent C-H bond activation carboxylation reaction.
Separation of disaccharide epimers, anomers and connectivity isomers by high resolution differential ion mobility mass spectrometry
Authors: Mastellone Jordan , Kabir K M Mohibul , Donald William
Published: February 2022

Glycans are ubiquitous, structurally diverse molecules that have specific and general roles involving metabolism, structure, energy storage, and cell-to-cell signalling. Functional specificity depends strongly on the complexity of structures that polysaccharides can adopt based on their subunit composition, length, extent of branching, glycosidic bond connectivity and anomeric configuration. However, the rapid, sensitive, and comprehensive characterization of glycan isomers can be challenging owing to limitations associated with their separation. Here, ten composition, anomeric and connectivity disaccharide isomers were separated and detected using high-resolution differential ion mobility-mass spectrometry (DMS-MS, also known as FAIMS). Focus was primarily directed to compositional isomers corresponding to epimers that differ by the axial or equatorial position of a single hydroxyl group. DMS resolving power was enhanced 15-fold primarily by increasing the fraction of helium in the ion carrier gas and lowering the flow rate. DMS-MS of each disaccharide resulted in surprisingly complex and unique multi-peak spectra with up to ten fully and partially resolved peaks for β-1,4-mannobiose (Man-1,4β-Man). Each DMS spectrum has at least one differentiating peak that is not in the other spectra, indicating that DMS can be used to fully or partially resolve composition, configuration and connectivity isomers. Thus, DMS-MS has the potential to be used for identifying polysaccharide isomers in a spectral ‘fingerprinting’ approach. The integration of high-resolution DMS into high-throughput MS-based glycomics and glycoproteomics workflows may be useful in the future for improving the characterization of glycans and glycosylated biomolecules.
Real-time Prediction of 1H and 13C Chemical Shifts with DFT accuracy using a 3D Graph Neural Network
Authors: Guan Yanfei , Sowndarya SV Shree , Gallegos Liliana , St. John Peter , Paton Robert
Published: February 2022

The computational prediction of NMR chemical shifts using quantum mechanical calculations is now commonplace in aiding organic structural assignment since spectra can be computed for several candidate structures and then compared with experimental values to find the best possible match. However, the computational demands of calculating multiple structural- and stereo-isomers, each of which may typically exist as an ensemble of rapidly-interconverting conformations calculations, are expensive. In this work, we address both of these shortcomings by developing a rapid machine learning (ML) protocol to predict 1H and 13C chemical shifts through an efficient graph neural network (GNN) using 3D structures as input. Transfer learning with experimental data is used to improve the final prediction accuracy of a model training using QM calculations. When tested on the CHESHIRE dataset, the 13C chemical shifts are predicted with comparable accuracy to the best-performing DFT functionals (1.5 ppm) in around 1/6000 of the CPU time.
Exploring the Relationship between the CO Oxidation Reaction and the Elemental Composition in Electrocatalysts with Machine Learning - a Case Study of PtRuPdRhAu High Entropy Alloys
Authors: Mints Vladislav , Pedersen Jack , Bagger Alexander , Quinson Jonathan , Anker Andy , Jensen Kirsten , Rossmeisl Jan , Arenz Matthias
Published: February 2022

In recent years, the development of complex multi-metallic nanomaterials like high entropy alloy (HEA) catalysts has gained popularity. Composed of 5 or more metals, the compositions of HEAs exhibit extreme diversity. This is both a promising avenue to identify new catalysts and a severe constraint on their preparation and study. To address the challenges related to the preparation, study and optimization of HEAs, machine learning solutions are attractive. In this paper, the composition of PtRuPdRhAu hydrogen oxidation catalysts is optimized for the CO oxidation reaction. This is achieved by constructing a dataset using Bayesian optimization as guidance. For this quinary nanomaterial, the best performing composition was found within the first 35 experiments. However, the dataset was expanded until a total of 68 samples were investigated. This final dataset was used to construct a random forest regression model and a linear model. These machine learned models were used to assess the relationships between the concentrations of the consituent elements and the CO oxidation reaction onset potential. The onset potentials were found to correlate with the composition dependent adsorption energy of *OH obtained from density functional theory. This study demonstrates, how machine learning can be employed in an experimental setting to investigate the vast compositional space of HEAs.
In vitro characterization of a nitro-forming oxygenase involved in 3-(trans-2’-aminocyclopropyl)alanine biosynthesis
Authors: Pang Linlin , Niu Weijing , Duan Yuwei , Huo Liujie , Li Aiying , Wu Jiequn , Zhang Youming , Bian Xiaoying , Zhong Guannan
Published: February 2022

In vitro characterization experiments revealed the formations of 3-(trans-2’-aminocyclopropyl)alanine ((3-Acp)Ala) and 3-(trans-2’-nitrocyclopropyl)alanine ((3-Ncp)Ala) are originated via two homologous proteins BelK and HrmI, which regioselectively catalyze Nε-nitration of L-lysine. The two enzymes belong to the emerging heme-oxygenase-like diiron oxidase and oxygenase (HDO) superfamily and the catalytic center of BelK is validated by homology modeling and site-directed mutations. Based on the in vitro characterization, the biosynthetic pathways of (3-Acp)Ala and (3-Ncp)Ala are first proposed.
Salt enrichment and dynamics in the interface of supercooled aqueous droplets
Authors: Kwan Victor , Maiti Shoubhik , Saika-Voivod Ivan , Consta Styliani
Published: February 2022

The interconversion reaction of NaCl between the contact-ion pair (CIP) and the solvent-separated ion pair (SSIP) as well as the free-ion state in cold droplets have not been yet investigated. We report direct computational evidence that the lower the temperature the closer to the surface the ion interconversion reaction takes place. In supercooled droplets the enrichment of the subsurface in salt becomes more evident. The stability of the SSIP relative to the CIP increases as the ion-pairing is transferred toward the droplet's outer layers. In the free ion form, the number density of Chloride ion in nanodroplets shows a broad maximum in the interior in addition to the well-known maximum in the surface. In the study of the reaction dynamics, we find a weak coupling between the interionic NaCl distance reaction coordinate and the solvent degrees of freedom, which contrasts the free energy diffusive barrier crossing found in bulk solution. The water self-diffusion coefficient is found to be at least an order of magnitude larger than that in the bulk solution. We propose to exploit the enhanced surface ion concentration at low temperature to eliminate salts from droplets in native mass spectrometry ionization methods. Reduction of adduct formation between macromolecules and salt may open up the possibility to directly ionize a biological sample from a physiological solution in experiments.
Solvent-Mediated Charge Transfer Dynamics of a Model Brown Carbon Aerosol Chromophore: Photophysics of 1-Phenylpyrrole Induced by Water Solvation
Authors: Peterson Brianna , Alfieri Megan , Hood David , Hettwer Christian , Costantino Daniel , Tabor Daniel , Kidwell Nathanael
Published: February 2022

Nitrogen heterocycles are known to be important light-absorbing chromophores in a relatively new class of aerosols, commonly referred to as ‘brown carbon’ (BrC) aerosols. Due to their significant absorption and spectral overlap with the solar actinic flux, these BrC chromophores steer the physical and optical properties of aerosols. To model the local aqueous solvation environment surrounding BrC chromophores, we generated cold molecular complexes with water and a prototypical BrC chromophore, 1-phenylpyrrole (1PhPy), using supersonic jet-cooling and explored their intermolecular interactions using single-conformation spectroscopy. Herein, we utilized resonant two-photon ionization (R2PI) and UV holeburning (UV HB) double-resonance spectroscopies to obtain a molecular-level understanding of water microsolvation’s role in charge transfer upon photoexcitation of 1PhPy. Quantum chemical calculations and one-dimensional discrete variable representation simulations revealed insights into the charge transfer efficacy of 1PhPy with and without single water molecule addition. Taken together, our results indicate that the intermolecular interactions with water guide the geometry of 1PhPy to adopt a more twisted intramolecular charge transfer (TICT) configuration, thus facilitating charge transfer from the pyrrole donor to the phenyl ring acceptor. Fluorescence measurements with increasing H2O %volume corroborated our gas-phase studies by indicating that a polar water solvation environment stabilizes the TICT configuration of 1PhPy in the excited electronic state, from which emission is observed at lower energy compared to the locally-excited configuration.
Chemical Bonding Origin of Glass Formation in Metal-Organic Frameworks
Authors: Sarkar Sounak , Egede Grønbech Thomas Bjørn , Mamakhel Aref , Bondesgaard Martin , Sugimoto Kunihisa , Nishibori Eiji , Iversen Bo Brummerstedt
Published: February 2022

Glass-forming metal organic frameworks (MOFs) have novel applications, but the origin of their peculiar melting behavior is unclear. Here, we report synchrotron X-ray diffraction electron densities of two zeolitic imidazolate frameworks (ZIFs), the glass-forming Zn-ZIF-zni and the isostructural thermally decomposing Co-ZIF-zni. Electron density analysis shows that the Zn‒N bonds are more ionic than Co‒N bond, which have distinct covalent features. Variable temperature Raman spectra reveal onset of significant imidazolate bond weakening in Co-ZIF-zni above 673 K. Melting can be controlled by tuning the metal–ligand and imidazole bonding strength as shown from nine solid solution structures of CoxZn1-x-ZIF-zni (x = 0.3 to 0.003) were synthesized, and a mere 4% Co-doping into Zn-ZIF-zni results in thermal decomposition instead of melting. These findings advocate significant chemical space for de-signing new MOF glasses either by engineering the chemical bonding with ligand functionalization or by avoiding defects at the metal site in the crystal lattice.
TRANSFORMASI CERITA ENDANG RARA TOMPE DALAM PERTUNJUKAN KETHEK OGLENG PACITAN
Authors: Mustofa Arif , Hendriyanto Agoes , Sutopo Bakti
Published: February 2022

This research aims to: 1) describe the plot of Endang Roro Tompe story and Kethek Ogleng performance art; 2) describe the transformation process of Endang Roro Tompe story into Kethek Ogleng performance art. The data were collected by these four steps: 1) observing Kethek Ogleng performance art, 2) recording the video and audio of Endang Rara Tompe’s story ; 3) describing the video recording based on the performance and transcribing the audio recording of Endang Roro Tompe. The result shows that Kethek Ogleng performance art is influenced by the plot of Panji Endang Rara Tompe. However, in the whole story, the performance only takes several scenes: The monkey comes, the monkey meets Endang Rara Tompe, the monkey falls in love with Endang Rara Tompe, and the monkey leaves back to the kingdom. There are two changing patterns from Endang Rara Tompe’s hypogram into Kethek Ogleng performance art. The first change deals with the cut of scenes. Kethek Ogleng performance art only explains the end of Endang Rara Tompe’s story. The story of Jenggala Kingdom is omitted in Kethek Ogleng performance art. The second is changing the main character. The author changes the main character from Dewi Sekartaji into Panji Asmarabangun or the monkey.Penelitian ini bertujuan untuk: 1) menghasilkan deskripsi pola alur Cerita Endang Rara Tompe dan pertunjukan Kethek Ogleng; 2)menghasilkan deskripsi proses transformasi dari Cerita Endang Rara Tompe ke pertunjukan Kethek Ogleng. Data dikumpulkan dengan cara: 1) pengamatan pertunjukan Kethek Ogleng; 2) perekaman  video pertunjukan Kethek Ogleng dan perekaman audio cerita Endang Rara Tompe; 3) pendeskripsian struktur pertunjukan pertunjukan; pentranskripsian hasil rekaman cerita Endang Rara Tompe. Analisi data dilakukan dengan cara 1) menyusun struktur pertunjukan (visual) Kethek Ogleng; 2) menyusun struktur cerita (lisan) Endang Rara Tompe; 3) membandingkan struktur pertunjukan (visual) Kethek Ogleng dengan struktur cerita (lisan) Endang Rara Tompe; 4) menganalisis pola perbedaan dan persamaan antara bentuk lisan dan bentuk visual. Hasil analisis menunjukkan bahwa struktur pertunjukan Kethek Ogleng dipengaruhi oleh pola alur cerita Panji Endang Rara Tompe. Namun, secara keseluruhan kisah, hanya diambil beberapa pertistiwa saja yaitu: kemunculan kera, pertemuan kera dengan Endang Rara Tompe, adegan jatuh cinta, dan adegan kembali ke kerajaan. Terdapat dua pola pemindahan dari hipogram Cerita Endang Rara Tompe ke pertunjukan Kethek Ogleng. Pertama yaitu pemotongan Adegan. Pertunjukan Kethek Ogleng hanya berisi bagian akhir dari  cerita Endang Rara Tompe. Adegan kerajaan Jenggala tidak dimunculkan dalam pertujukan Kethek Ogleng. Keduaya itu alih tokoh utama. Pengarang mengubah tokoh utama dari Dewi Sekartaji menjadi Panji Asmarabangun atau tokoh kera.
PHONETIC GRAMMAR OF PLOSIVES SOUNDS SPOKEN BY SUNDANESE AND JAVANESE
Authors: Irawan Yusup , Riani NFN
Published: February 2022

This study aims to identify “the phonetic grammar" of voiced plosive sounds [b, d, and g] and voiceless [p, t, and k] at the initial position of the words uttered by two different groups of native speakers: Sundanese and Java. These sounds are phonemically the same phonemes in Sundanese, Javanese and Indonesian. The findings show that the two groups of native speakers realize different and the same VOT (Voice Onset Time) pattern of popping sounds. For sounds voiced plosives or lenis plosive [b, d, and g], Sundanese speakers realize it with a negative VOT pattern, while Javanese speakers do it with a positive VOT pattern. Then, voiced plosive sounds uttered by Javanese speakers tend to be "aspirated" or breathy. For the voiceless plosives or fortis plosives [p, t, and k], the two groups of speakers pronounce them in the same pattern, namely the positive VOT pattern, and even tend to have zero VOT. The VOT patterns reflect aspirated voiced and voiceless phonation categories for Javanese and voiced and voiceless for Sundanese.Penelitian ini bertujuan untuk mengidentifikasi gramatika fonetik “phonetic grammar” bunyi-bunyi letupan bersuara [b, d, dan g] dan tak bersuara [p,t, dan k]  pada posisi awal kata yang diucapkan oleh dua kelompok penutur jati yang  berbeda: Sunda dan Jawa. Bunyi-bunyi itu secara fonemik merupakan fonem yang sama dalam bahasa Sunda, Jawa, dan Indonesia. Temuan dalam penelitian ini adalah kedua kelompok  penutur jati merealisasikan pola VOT (voice onset time) bunyi letupan yang berbeda dan sama. Untuk bunyi-bunyi bersuara plosive lenis  [b, d, dan g] penutur bahasa Sunda merealisasikannya dengan pola VOT negatif, sedangkan penutur bahasa Jawa merealisasikannya dengan pola VOT positif. Kemudian bunyi-bunyi letupan bersuara yang diucapkan oleh penutur bahasa Jawa cenderung “beraspirasi” atau breathy. Pada bunyi-bunyi takbersuara atau plosive fortis  [p, t, dan k], kedua kelompok penutur mengucapkannya dengan pola yang sama, yakni pola VOT positif bahkan cenderung ber-VOT nol atau zero. Pola-pola VOT itu merefleksikan kategori fonasi bersuara breathy dan takbesuara untuk bahasa Jawa dan bersuara dan tak bersuara untuk bahasa Sunda.
KAJIAN MAKNA DAN FUNGSI TEMBANG BAWA METRUM DANDANGGULA DALAM LAGU CAMPURSARI
Authors: Setyawan Bagus Wahyu , Raharjo Yusuf Muflikh
Published: February 2022

Bawa as a one of literary song like a sindhenan, janturan, gerongan, and palaran. Firstly bawa song used in Javanese traditional or karawitan music, but since 1970th bawa song start to used in other genre, such as campursari. This research aimed to describe and analyse the meaning and function of bawa song in campursari. Sample on this research taken from bawa song with dandanggula poetic meter, that are bawa of kanca tani, pepeling, and nyidham sari song. Data collected technique using record-note and in-depth interview with some informant. Data analysis of this research using qualitative-interactive with the phase are data reduction, data display, and conclusion drawing. Result of this research find that bawa on campursari song have function as intro before song sing in. Therefore, bawa also represented the meaning and message of the campursari song. So, the lyric of bawa song have suitability with content of campursari song. Bawa song in this era also have attract power on campursari fans, because there are some dialogue between bawa singer with other singer, MC, or some audience which contain sense of joke inside.Bawa merupakan salah bentuk sastra tembang seperti halnya sindhenan, janturan, gerongan, dan palaran. Awalnya bawa digunakan untuk musik-musik karawitan, tetapi mulai tahun 1970-an tembang bawa mulai merambah dalam genre musik campursari. Penelitian ini bertujuan untuk menganalisis makna dan fungsi tembang bawa dalam lagu campursari. Sampel yang digunakan adalah tembang bawa bermetrum dandanggula, yaitu bawa langgam kanca tani, pepeling, dan nyidham sari. Pengumpulan data menggunakan teknik simak-catat dan wawancara mendalam dengan narasumber. Analisis data dalam penelitian ini menggunakan analisis interaktif kualitatif dengan tahapan reduksi data, sajian data, dan penarikan simpulan. Hasil dari penelitian ini ditemukan bahwa tembang bawa dalam lagu campursari berfungsi sebagai intro atau awalan sebelum masuk lagu. Selain itu bawa juga merepresentasikan makna atau kandungan isi dari lagu campursari. Jadi, lirik tembang bawa memiliki kesepadanan dan kesesuaian makna dengan isi dari lagu campursari. Tembang bawa di era sekarang juga menjadi daya tarik bagi penikmat lagu campursari, karena terdapat dialog antara pelantun bawa dengan penyanyi lain, MC, bahkan dengan penonton yang kerap kali mengandung unsur humor.
Kalimate (calcium polystyrene sulfonate) and bowel perforation – a cause not to be ignored
Authors:   Carolina Marques, Cátia Ferreira, Rita Marques, Ricardo Vaz-Pereira, Urânia Fernandes, Gonçalo Guidi, João Pinto-deSousa
Published: February 2022

Calcium polystyrene sulfonate (CPS), also known as Kalimate, is a cationexchange resin (CER), commonly used to treat hyperkalemia. A case of a patient with chronic kidney disease (CKD) who underwent right hemicolectomy for colonic perforation due to intestinal necrosis secondary to oral CPS administration is presented. The histopathological findings confirmed the colonic ischemia and perforation and showed a luminal deposition of crystals with a fish scale pattern, compatible with CER (Kalimate). This report aims to present and discuss this unusual case considering the most updated scientific evidence.
Investigating the Effect of Gradation, Temperature and Loading Duration on the Resilient Modulus of Asphalt Concrete
Authors: Junaid Muhammad , Ali Shah Muhammad Zafar , Yaseen Ghulam , Awan Hammad Hussain , Khan Daud , Jawad Muhammad
Published: February 2022

This research was carried out to assess the effect of aggregate skeleton, temperature variation, and loading duration on the resilient modulus of asphalt concrete mixtures. Two different gradation methods, i.e., the conventional method of gradation and the Bailey method of gradation, were adopted to design the aggregate skeleton. The effect of these gradation methods, with temperature and loading duration, on the resilient modulus of asphalt concrete has not been previously investigated. The Modified Marshall Test was used to determine optimum binder content against 4% air voids, and then volumetric and strength parameters were calculated against optimum binder content. For performance tests, specimens were prepared at optimum binder content using a Superpave gyratory compactor. An indirect tensile strength test on both types of mixtures was conducted, and a 20% value of indirect tensile strength was kept for peak load, whereas 10% was kept for seating load for conducting resilient modulus tests. The tests were conducted at 100 and 300 ms duration loads under two different temperatures, i.e., 25 oC and 40 oC. The results declared that aggregate skeleton, temperature, and loading duration have a prominent effect on the resilient modulus of asphalt concrete mixtures. Bailey gradation mixtures disclosed higher resilient modulus values than conventional gradation mixtures. Higher values of resilient modulus were observed for both gradation mixtures at low temperatures and under small duration loads than at high temperatures and large duration loads. The results of the two-way factorial design also confirmed the above findings. Doi: 10.28991/CEJ-2022-08-02-07 Full Text: PDF
THE IMPACT OF DIGITALIZATION OF THE ECONOMY ON THE DEVELOPMENT OF ACCOUNTING
Authors: Orlova Ekaterina , Isaeva Dar'ya
Published: February 2022

This scientific article discusses the current trends in the development of accounting methods. The advantages and disadvantages of the introduction of information technologies into the accounting structure are also considered and analyzed. Based on the analysis and research carried out, possible directions for the development of accounting under the influence of the comprehensive application of digital technologies are highlighted.
Cluster approach to regional consumer cooperation
Authors: Mel'nikov Vasiliy
Published: February 2022

The relevance and novelty of considering the regional cooperative cluster in the context of the consumer cooperation system is aimed at studying the possibility of its formation for the development of the consumer cooperation system of the region. Variants of definitions of the cluster are considered, the main characteristics of the cluster are highlighted, a generalized definition of the cluster is formulated, the main characteristics of the consumer cooperation system are highlighted, the characteristics of the cluster and consumer cooperation are compared, the characteristics of the consumer cooperation system are analyzed, the definition of the economic cluster of consumer cooperation is derived.
Definition of the term “corporation” in the Russian economic practice
Authors: Otaraeva Madina
Published: February 2022

Corporations as the main and largest economic entities with peculiar features differentiating them from other forms of conducting business activities legally and economically have acquired special significance both in the internal economy and in the global transnational economic relations. It is utterly important to approach the definition of corporations from different angles which will facilitate a better understanding of the underlying characteristics of corporate structures. The article provides a comprehensive analysis of the term “corporation” in a formal sense and in the context of the Russian economic practices.
A Scalable and Efficient Port-Based Adaptive Resource Monitoring Approach in Software Defined Networks
Authors: ÖZER Hasan , OKUMUŞ İbrahim Taner
Published: February 2022

The need for communication tools is increasing from the past to the present, therefore the tools and methods in network technologies are evolving. Depending on this development, network scale and complexity increase and the limitations of traditional network technology are surfaced. Software-defined Network (SDN) provides a variety of opportunities for the management and optimization of these challenges. Network resource monitoring is very important for providing information to network applications. This study introduces an adaptive port-level bandwidth monitoring method designed for SDN networks. The proposed approach uses a polling-based monitoring paradigm. There is a trade-off between measurement accuracy and monitoring overhead. With this adaptive method, it is aimed to decrease the overhead while maintaining an acceptable level of accuracy of the measurements and also to use network resources more efficiently. The proposed adaptive monitoring approach has 46% less overhead than the periodic polling method and 6.7% less overhead than the PayLess approach. At the same time, this approach is 5.4% more accurate than the periodic polling approach.
A NEW COPPER TERNARY COMPLEX IS A PROMISED COMPOUND FOR THE TREATMENT OF TRIPLE-NEGATIVE BREAST CANCER
Authors: Lima Paula Marynella Alves Pereira , Brandão Douglas Cardoso , Cruz Raquel Pereira , Orsolin Priscila Capelari , Guerra Wendell , Goulart Luiz Ricardo , Oliveira Júnior Robson José de , Araújo Thaise Gonçalves
Published: February 2022

Objectives: Triple-negative breast cancer (TNBC) is a biologically aggressive tumor with poor prognosis due to the lack of effective therapeutic strategies. Although chemotherapy is widely employed, chemoresistance and severe side effects remain a challenge in controlling this breast cancer subtype. Doxorrubicin (DOX) and platinum-based drugs are commonly used in oncological regimens but with limitations. In this scenario, metallodrugs based on copper element have been emerged as novel and promised compounds, due to the presenting mechanisms of action and biodistribution different from the platinum drugs already used, and may be effective against tumors that are resistant to conventional chemotherapy. This study focuses on assessing the cytotoxic effect of new copper ternary metal complex (CBP-01) on breast cancer tumor cells. Methodology: Cell viability of human breast cell lines, MCF 10A (non-neoplastic) and neoplastic cells, MCF7, T-47D, and MDA-MB-231, was evaluated by 3-[4,5-dimethylthiazole-2-yl]2,5-diphenyltetra-zolium bromide — MTT methodology. CBP-01 was tested in different concentrations (1, 5, 10, 12.5, 25, and 50 μM) for 24, 48, and 72 h, and the cellular responses were compared with Carboplatin (CARB), Cisplatin (CIS), and DOX. Results: The dose-dependent profile was identified for the four drugs and the cell viability differed between the times of treatment. CBP-01 was effective against the tumor cell lines. Regarding the triple-negative cell line (MDA-MB231), CBP-01 was clearly more effective with lower IC50 (2.05) and higher SI (3.10) than the other compounds. Conclusion: Our data provide new prospects for TNBC treatment and may yield new directions for tumor management.
THE INFLUENCE OF THE NAVIGATING NURSE BEFORE THE DIAGNOSIS AND START OF TREATMENT OF PATIENTS AFFECTED BY BREAST CANCER IN THE CITY OF GOIANIA (GO), BRAZIL
Authors: Queiroz Bruna Gonçalves , Freitas-Junior Ruffo
Published: February 2022

Objective: To evaluate and measure the time reduction in days between diagnosis and the start of treatment in patients guided by the navigating nurse or in patients attending outpatient clinics in a cancer referring Hospital. Methodology: This is a retrospective, analytical cohort study. The study was carried out in a specialized cancer hospital located in the city of Goiânia, GO. Data collection was performed at the Gynecology and Breast Service (SGM), using the data available in the medical records of women who were seen for the first time during the period from August 2018 to July 2019. Patients who met the eligibility criteria were classified into two groups (i.e., navigated and un-navigated). The data were analyzed using the SPSS version 23 statistical package, adopting a significance level of 5% (p<0.05), and the nonparametric test (Mann– Whitney U-test). Results: In total, 59 patients were included in the study. The patients aged 40–59 years (50.8%). There was a significant reduction in the mean delay in the group of patients guided by the navigating nurse: between the first consultation until the procedure (biopsy) for the diagnosis of breast cancer performed from 82.97 (SD 131.99) to 19.05 (SD 32.84) days, p=0.023; from the first consultation to the biopsy result from 105.41 (SD 137.94) to 30.95 (SD 36.92) days, p=0.002; and from the procedure to the biopsy result from 22.43 (SD 17.42) to 11.91 (SD 10.09) days, p=0.002. Conclusion: The performance of the navigator nurse provided an important reduction in different time intervals, allowing greater agility in the assistance and management of women with breast cancer, in a cancer referral hospital.
HEREDITARY BREAST AND OVARIAN CANCER PATIENTS HAVE A FAMILY HISTORY OF CANCER OUTSIDE THE SPECTRUM OF THE SYNDROME, MIMICKING LYNCH AND LI–FRAUMENI SYNDROMES
Authors: Lacerda Elisângela de Paula Silveira , Goveia Rebeca Mota , Silva Paula Francinete Faustino , Teixeira Thais Bonfim , Freitas-Junior Ruffo de
Published: February 2022

Patients with pathogenic variants (PV) in the BRCA1 and BRCA2 genes have hereditary breast and ovarian cancer syndrome (HBOC). Some patients with HBOC have a family history (FH) of different types of cancer not related to the syndrome. The objective of this study was to observe the FH profile of cancer in patients with HBOC syndrome. A total of 123 patients treated at the Advanced Breast Diagnostic Center (CORA) with clinical criteria suggestive of HBOC syndrome were selected according to the National Comprehensive Cancer Network (NCCN). The collection of 4 ml of blood was performed, which was subjected to DNA extraction and PV analysis in the BRCA1 and BRCA2 genes by next generation sequencing. The data were analyzed using the Sophia DDM and Ion Reporter software. The variants were considered to be pathogenic according to the ACMG criteria. It was found that among 123 patients analyzed, 19 had HBOC syndrome, of whom 5 were related. Thus, we had 16 families with HBOC syndrome. Among the 16 families, 14 (87.5%) had FH from cancers related to HBOC syndrome, 9 (56.25%) had FH from cancers not related to HBOC syndrome, and 1 (16.25%) did not have FH cancer. A total of 8 (50%) of families with HBOC also met the NCCN criteria for other hereditary cancer syndromes, 3 (18.75%) for Li–Fraumeni syndrome (LFS) and HBOC, 3 (18.75%) for Lynch syndrome (LS) and HBOC, and 2 (12.5%) for HBOC, LFS, and LS. The most common cancers observed outside the common spectrum of HBOC syndrome in families were stomach cancer (25%), intestine (18.75%), liver (18.75%), and skin (18.75%). These data suggest the importance of a complete assessment of FH in patients with HBOC syndrome to better understand its relationship with the predisposition to different types of cancer.
EVALUATION OF BONE MINERAL DENSITY LOSS IN PATIENTS WITH BREAST CANCER USING AROMATASE INHIBITORS AS ADJUVANT ENDOCRINE THERAPY: 5-YEAR FOLLOW-UP
Authors: Antonini Marcelo , Salerno Gisela Rosa Franco , Vieira Natalia Daniela Kovalinski , Cardoso Mariana Soares , Solino Matheus de Paula , Ferraro Odair , Lopes Reginaldo Guedes Coelho
Published: February 2022

Objective: To verify the impact of the use of aromatase inhibitors in postmenopausal women undergoing treatment for breast cancer, to evaluate the progression to osteopenia and osteoporosis, and to assess bone loss. Methodology: This is a cohort, prospective study with 76 women with positive hormone receptor (RH+) breast cancer before and after the beginning of the use of aromatase inhibitors (AI). After approval of the project by the ethics committee, the mineral density of the lumbar spine (L1–L4), the neck of the femur, and the total femur were analyzed by image examination and the average standard deviation for the young adult (T-score) was calculated in all patients before and after 6 months and 5 years of the use of AI by classifying them into three groups: osteoporosis, osteopenia, and normal. The data were analyzed initially by the KS test to determine the normality of the sample and later by ANOVA considering p≤0.05. Results: Before the use of AI, 38 (54%) patients had a normal exam, and 32 (45%) had osteopenia and no osteoporosis. After 6 months of treatment, 34 (49%) had normal examination, 30 (43%) had osteopenia, and 6 (8%) had osteoporosis; after 5 years, 26 (37%) had normal examination, 38 (55%) had osteopenia, and 6 (8%) had osteoporosis; no patient with normal bone density developed osteoporosis. There was a significant loss of bone mass in the femur of -7.88 after 5 years (p=0.001), in the femoral neck of -5.76 after 6 months (p=0.019) and -9.41 after 5 years (p=0.000). There was no significant change in the column (p=0.054). Conclusion: Bone loss in postmenopausal women after 6 months and 5 years may be related to the use of aromatase inhibitors.
HIGH NEUTROPHIL-TO-LYMPHOCYTE RATIO IS PROGNOSTIC FACTOR IN EARLY-STAGE BREAST CANCER PATIENTS
Authors: Orlandini Leonardo Fleury , Pimentel Franklin Fernandes , Andrade Jurandyr Moreira de , Reis Francisco José Cândido dos , Arruda Leticia De Mattos- , Tiezzi Daniel Guimarães
Published: February 2022

Objectives: We aimed to explore the association of a readily available biomarker of systemic inflammation, the neutrophil-to-lymphocyte ratio (NLR), with breast cancer survival. Methodology: We undertook a single-centered retrospective study of patients with stages I–III breast cancer from 1999 to 2013. Clinicopathological data were collected before receiving any type of treatment. Survival analysis was performed using Cox regression models and Kaplan–Meier curves. Results: The cutoff value for NLR was set at 4.0 (NLRhigh ≥ 4 and NLRlow < 4). Of 1,700 patients included in this study, 121 (7%) had NLRhigh. Median for NLRhigh was 5.0 (4.0–34) and 1.9 (0.18–3.99) for NLRlow. Patients with NLRhigh were associated with more stage III at diagnosis (55% vs. 36%, p <0.01). Kaplan–Meier curves with log-rank tests at 10 years revealed a significant shorter disease-free survival (DFS) (p=0.02) and worse overall survival (OS) (p<0.001) for women with NLRhigh compared to those with NLRlow. Multivariate analysis revealed that NLR greater than 4 was independently correlated with shorter OS (HR 2.09, 95%CI 1.02–4.2, p=0.04). Furthermore, a subgroup of obese women with NLRhigh (classified as body mass index ≥30 kg/m2 ) had the shortest DFS and the worst OS in the cohort (p<0.001). Conclusion: Pretreatment NLR greater than 4 was correlated with worse prognosis in breast cancer. Interestingly, a subgroup of obese patients with NLRhigh had the shortest survival, showing the state of chronic inflammation observed in obese women may influence immune system and the prognosis in breast cancer. Prospective studies are needed to define the best cutoff values and introduce this inflammatory biomarker in clinical use.
CLINICAL AND PATHOLOGICAL CHARACTERISTICS AND MOLECULAR SUBTYPES IN A PROSPECTIVE COHORT OF PATIENTS WITH BREAST CANCER ACCORDING TO ACCESS TO TREATMENT: SUPPLEMENTARY HEALTH CARE VERSUS UNIFIED HEALTH SYSTEM
Authors: Gomes Filho José Euderaldo Costa , Rocha Ariane Silva da , Fernandes Gisele Aparecida , López Rossana Verónica Mendoza , Curado Maria Paula
Published: February 2022

The aim of this study was to describe the clinical and pathological characteristics and molecular subtypes in a prospective cohort of patients with breast cancer based on access to treatment — Supplementary Health Care versus Unified Health System (UHS). This is a cross-sectional study aligned to a prospective cohort developed at Hospital AC Camargo Cancer Center with 705 female patients, aged between 18 and 93 years and diagnosed with breast cancer. They had access to treatment by Supplementary Health (56.5%, n=398). Tumor topography for both UHS and Supplementary Health group include higher right breast, 53.4% (n=164) and 50.8 (n=202) (p=0.226); sublocation in the upper outer quadrant, 40.4% (n=124) and 52.3% (n=208) (p<0.001); T1 clinical staging, 37.8% (n=116) and 42.2% (n=168) (p<0.001); N0, 50.5% (n=155) and 54.3% (n=216) (p=0.109); and M0, 95.1% (n=292) and 93.5% (n=372) (p=0.667), respectively. For both UHS and Supplementary Health, pathological classification T1, 44.6 (n=137) and 46% (n=183) (p<0.001); the presence of regional lymph nodes and distant metastasis showing no difference in N0, 59.6% (n=183) and 54.8% (n=218) (p=0.451); M0, 93.8% (n=288) and 95% (n=378) (p=0.306); invasive ductal carcinoma, 81.4% (n=250) and 84.9% (n=338) (p<0.001); histological grade 2, 42.7% (n=131) and 44.5 (n=177) (p<0.001); nuclear grade 3, 60.3% (n=185) and 59.5% (n=237) (p=0.421); HER2 negative, 73.2% (n=216) and 79% (n=313) (p<0.001); estrogen positive, 80.4% (n=246) and 76.9% (n=306) (p=0.228); progesterone positive, 80.4% (n=246) and 76.9% (n=306) (p=0.280); Ki-67 positive, 99.6% (n=278) and 100% (n=393) (p<0.001); and molecular classification defined as Luminal B, 56.8% (n=167) and 50% (n=328), respectively. Access to treatment by UHS or Supplementary Health demonstrated significant difference in tumor sublocation, clinical and pathological T staging, morphology, histological grade, HER2, and Ki76, whereas there was no difference for clinical and pathological N and M staging, nuclear grade, estrogen, progesterone, and molecular classification.
UNIJA TRI REPUBLIKE. MIROVNI PLAN ZA BOSNU I HERCEGOVINU IZ 1993. GODINE
Authors: Nikolić Kosta
Published: February 2022

U tekstu se piše o planu za okončanje rata u Bosni i Hercegovini koji je razmatran od juna do decembra 1993. godine. Mirovni plan modelirale su Ujedinjene nacije i Evropska unija preko svojih posrednika. Osnovna ideja podrazumevala je stvaranje tri republike u Bosni i Hercegovini, čime je napušten koncept multietničke države. Akcenat je stavljen na analizu stavova sukobljenih strana, uključujući i Srbiju i Hrvatsku, i traženje odgovora na pitanje da li je to bio plan koji je mogao da zaustavi rat i istoriju Bosne i Hercegovine povede u drugom smeru.
THE PROBLEM OF THE HISTORIZATION OF 20TH CENTURY SERBIAN FASHION 1920-1980
Authors: Žarić Stefan
Published: February 2022

The paper covers the history of 20th century Serbian fashion from the 1920s through the 1980s, focusing on the problem of its historization. Based on established readings submitting 20th century Serbian fashion to politics thus distancing it from global fashion history, I aim to structure a possible historical narrative of fashion by identifying the elements of haute couture in 20th century Serbian fashion industry. Rather than contrasting Serbian fashion figures with their Western counterparts and deepening the West / East Europe fashion divide, the paper traces similarities between them, demonstrating that 20th century Serbian fashion responded to haute couture trends simultaneously with their emergence in the West.
STRAH ILI REALNOST? MOGUĆNOST SOVJETSKE VOJNE INTERVENCIJE U JUGOSLAVIJI 1948–1953.
Authors: Životić Aleksandar
Published: February 2022

U radu se na osnovu dostupnih objavljenih i neobjavljenih arhivskih izvora prevashodno sovjetskog i jugoslovenskog porekla, kao i relevantne istoriografske i memoarske literature analizira pitanje postojanja sovjetskih namera za vojnu intervenciju u Jugoslaviji u vreme sukoba između nje i zemalja Informbiroa. Predstavljene su ekonomske i demografske okolnosti koje su uticale na kreiranje sovjetskog pristupa razvoju sopstvenih i „satelitskih“ vojnih snaga. Posebno su razmatrane promena geopolitičkog položaja Jugoslavije usled sukoba s ranijim saveznicima i vojnog i političkog približavanja zapadnom svetu, kao i zapadna percepcija jugoslovenske vojne ugroženosti i sposobnosti jugoslovenskih oružanih snaga da se odupru eventualnoj sovjetskoj agresiji.