bluuebunny/crossref_metadata_2025 huggingface dataset:
Sociocultural features of the Arabic academic discourse
Authors: Alhaded Hashem Hani Shehadeh , Shavtikova Aurika , Merai Mariam
Published: April 2022

The Arabic academic discourse is a complex organism associated with the linguistic, national, cultural and religious characteristics of the inhabitants of the Middle East. The article is interdisciplinary in nature and can be considered from the point of view of sociolinguistics, comparative linguistics and psycholinguistics. The subject of the study is the social and cultural features of the Arabic academic discourse. The object of research is academic discourse implemented in Arabic. The purpose of this article is to identify the key features of the Arab academic discourse and the degree of influence of globalization on it. The methodological basis of the study was the results of a survey of ArabicвЂ“speaking native students studying at the bachelor's and master's degrees in the Levant countries. The novelty of the research lies in the fact that the Arabic academic discourse in the Russian and international linguistic tradition is insufficiently studied, which entails communicative failures between communicants within the framework of Arabic academic discourse and global, international academic discourse. As a result of the study, the authors come to the conclusion that the Arabic academic discourse is a synthesis of traditional, national and religious foundations of the Arabic-speaking society; the teacher in the Arabic academic discourse takes an authoritarian position towards students. The research materials can be used in universities of the humanities in the study of special courses on intercultural communication, discoursology and a practical course of the Arabic language.
Addressing the Future with Data Visualization in Science Fiction Films: Dystopia or Utopia
Authors: Al-Mamori Yasir Khudeir Obid
Published: April 2022

The subject of the research is the methods and techniques of addressing the future in dystopian and utopian films. The object of research is visual effects and ways of displaying the future, which allow us to convey to the viewer the meaning of the narrative. In the process of research, special attention is paid to the possibilities of science fiction films that create another world with the help of special effects, emphasizing many themes and hidden ideas, while depicting a fairy tale. Special emphasis is placed on the fact that modern technologies, the possibilities of creating visual effects have changed the film industry, as a result of which it has strengthened the genre convergence of utopian and dystopian film products, as a result of which it has become possible to create plausible worlds so that science fiction films are perceived in a more immersive way. The main conclusions of the study are the conclusion that the modern tradition of visualizing science fiction films embraces and interweaves dystopias and utopias within the framework of one work, as a result of which the narratives are doubly fictional: they create a utopian or dystopian place as a backdrop for history, and at the same time the place itself becomes history. The author's special contribution lies in the fact that in the process of research, visual techniques of representing the future in cinematic fiction are highlighted, which invariably contain cultural meanings. The scientific novelty of the research is to identify and analyze the most typical techniques of reproducing the future in science fiction films using visual effects, which include brutalist architecture, creating an image of the future city.
Protestas y saqueos ante el “gasolinazo” mexicano de 2017
Authors: Moreno Velador Octavio Humberto , Díaz Herrera Gerardo
Published: April 2022

En este trabajo se analizan y comparan las protestas sociales y saqueos que sucedieron entre el 31 de diciembre de 2016 y el 8 de enero de 2017 en el contexto de un aumento a los precios de las gasolinas en México. Se presenta una reconstrucción de ambos fenómenos, así como algunos elementos estadísticos de su incidencia en todo el país; conceptualmente proponemos una distinción entre saqueos deliberadamente vinculados con la protesta, y aquellos no deliberadamente vinculados a ésta para distinguir y clasificar estos fenómenos. Finalmente, sugerimos que el auge súbito de los saqueos tuvo una posible función disuasoria para la continuidad de las protestas, así como también de legitimidad para el ejercicio de la fuerza pública en un contexto de fuerte inestabilidad política y social.
Irritant contact dermatitis treated with constitutional homoeopathic medicine – A case report
Authors: Patel Avinash , Ram Hanuman
Published: April 2022

Contact dermatitis (CD) is a skin disorder characterised by papules and vesicles on an erythematous base. It is often precipitated by an exogenous cause and has a global prevalence of 1.7–6.3%. Irritant CD (ICD) is a type of CD caused by repeated exposure to irritants such as acids, alkalis and oxidants (chemical burns) or low-grade irritants such as soaps, detergents and solvents. Cases of ICD have been reported to be treated successfully with homoeopathic medicines. In this case, a male patient aged 55 years presented with the complaints of blackish-brown discolouration and thick lichenified lesion on the dorsal aspect of the left forearm with sticky thick discharge. Case taking and repertorisation done on the basis of totality of symptoms led to prescription of the constitutional homoeopathic medicine Sepia. The dose and the potency were modified per the patient’s requirements. The patient reported relief in all complaints; there was a significant change in the visual analogue scale for the itching and the dermatology life quality index. This case illustrates the utility of homoeopathic constitutional medication in treating chronic allergic dermatological conditions. Further, larger scale studies are required to enable generalisation of the findings.
GEOPOLITICAL SENTIMENTS OF THE DONETSK RESIDENTS IN CONDITIONS OF ARMED CONFLICT (2014–2021)
Authors: Benchuk Vitalii
Published: April 2022

The article analyzes the geopolitical orientations of the citizens of Donetsk, in the conditions of the hybrid aggression of the Russian Federation against Ukraine during 2014–2021. It was found out that the prewar period of pro-Russian sentiments of local residents expressed not in separatist ambitions, but in desire to join Russian political/economic projects. In the conditions of "Russian spring" these moods have not proved fundamental changes, as sociological surveys showed. Most of their participants did not aim to join their region to an aggressor country. Further aggravation of the military-political situation by the Kremlin has led to the separation of the Donetsk region in two territories controlled by the Ukrainian authorities and temporarily occupied. This affected the change in geopolitical sympathies. During 2015–2017, an equable commitment between the European Union and Eurasian Customs Union in the polls, with a significant proportion of neutral status, is observed. They are experiencing minor movements towards the growth of the European course. However, the opposite trend is observed in the future. This is due to socio-political events in Ukraine and the influence of hostile propaganda to the mass consciousness of Donetsk.
Implementasi Keputusan Menteri Kesehatan Republik Indonesia Nomor 128 Tahun 2004 Tentang Kebijakan Dasar Pusat Kesejatan Masyarakat
Authors: Parjiyana Parjiyana , Parjiyana
Published: April 2022

Penelitian ini bertujuan untuk mengetahui bagaimana implementasi Keputusan Menteri Kesehatan Republik Indonesia tersebut, yaitu berkaitan dengan pelaksanaan pelayanan di Puskesmas Kota Dumai. Penelitian ini termasuk ke dalam jenis penelitian kuantitatif, dengan teknik pengumpulan data utama melalui penyebaran angket kepada masyarakat sebagai objek pelayanan, di samping melalui observasi dan wawancara sebagai teknik pengumpulan data pendukungnya. Adapun Informan dalam penelitian ini adalah masyarakat yang menjadi objek pelayanan dan petugas Puskesmas sebagai informan pendukung. Dengan menetapkan beberapa indikator dalam melihat pelaksana pelayanan di Puskesmas Kota Dumai, seperti indikator tampilan fisik, reabilitas, responsif, jaminan dan empati, penelitian ini mendapati bahwa implementasi dari keputusan menteri tersebut dalam hal pelayanan di Puskesmas Kota Dumai adalah sudah dapat dikatakan atau masuk ke dalam kategori cukup terlaksana. Hal ini didasari oleh fakta bahwa secara umum pasien di Puskesmas Kota Dumai sudah memberi penilaian terhadap pelayanan di Puskesmas tersebut adalah cukup terlaksana, berdasarkan atas hal-hal seperti pelayanan yang ramah, sopan, cepat tanggap, penuh perhatian, serta tidak membeda-bedakan status sosial.
Evaluasi Pelaksanaan Peraturan Daerah Nomor 16 Tahun 2008 Tentang Organisasi Dan Tata Kerja Dinas Daerah Pada Dinas Tata Kota, Kebersihan Dan Pertamanan Kota Dumai
Authors: Wahyuni Sri , Wahyuni Sri
Published: April 2022

Penelitian ini bertujuan untuk mengevaluasi Pelaksanaan Peraturan Daerah nomor 16 tahun 2008 tentang Organisasi dan Tata Kerja Dinas Daerah Pada Dinas Tata Kota, Kebersihan dan Pertamanan kota Dumai antara pelaksanaan tugas pokok dan fungsi dibidang kebersihan dan pertamanan. Data penelitian ini dikumpulkan dengan metode surveyberdasarkan keadaan sebelum dan sesudah terbentuknya peraturan daerah nomor 16 tahun 2008 yang menggunakan teori evaluasi Menurut Talizuduhu Ndraha, Model Before – After, yaitu: perbandingan antara sebelum dan sesudah suatu tindakan/ perlakuan (treatment). Tolok ukurnya adalah kondisi sebelumnya. Metode penelitian bersifat analisiskuantitatif, data yang diperoleh berdasarkan jawaban kuesioner dari 33 orang responden dan dianalisis dengan mencari nilai rata-rata. Dari hasil penelitian ini ditemukan berdasarkan variabel yang diteliti menunjukkan ada hubungan yangpositif baik terhadap pelaksanaan sebelum maupun sesudah terbitnya peraturan daerah nomor 16 tahun 2008 tersebut dengan hasil 57,33 % Kurang terlaksana. Rekomendasi dari penelitian ini adalah (i) perlunya prosedur atau standarkerja yang bisa diimplementasikan oleh pegawai dalam hal pelaksanaan bidang kebersihan dan pertamanan, (ii) pentingnya kerjasama antara Dinas/ Badan dan Kantor agar tidak terjadi tumpang tindih (Overlapping), tarik ulur pekerjaan serta saling menyalahkan diharapkan dapat dihindari apabila ada kejelasan dari pelaksanaan berdasarkan tugas pokok dan fungsi terutama dalam hal pelaksanaan bidang kebersihan dan pertamanan.
Die Geburt einer Struktur: Zur 60. Wiederkehr der Aufstellung der Azulenformel durch Pfau und Plattner
Authors: Hansen Hans-Jürgen
Published: April 2022

The historical way is described, how Pfau and Plattner arrived at the right formula of the azulenes. Starting from the ketone fraction of vetiver oil, they were able to separate from this fraction two sesquiterpenoid bicyclie ketones which they named α -and β-vetivone. Especially β-vetivone attracted their attention, since itself as well as reduced forms of it gave, on dehydrogenation at high temperature in the presence of sulfur, selenium or palladium on charcoal, a new type of azulene which they called vetivazulene. Dehydrogenation experiments with a new compound that had originally been synthesized by W. Hückel et al. and possessed an anellated five-seven ring system led also to blue azulenes. This observation together with a number of further results allowed Pfau and Plattner to assign the right structure also to vetiv- and guaiazulene. Degradation experiments with β-vetivone and reduced forms of it suggested to assume a corresponding hydroazulene skeleton also for β-vetivone. 30 years later, J.A. Marshall et al. showed that the structure of β-vetivone had to be changed into a spiro[4.5]decane ring system, showing the same symmetry properties as the originally proposed cis-fused hydroazulene system.
Eco-Efficiency: A Prerequisite for Future Success
Authors: Glauser Manuel , Müller Peter
Published: April 2022

At Roche, eco-efficiency – the optimal use of material, energy, human resources, and capital to supply innovative products to the market – is considered as a prerequisite for business success in the future. Group-wide activities to rise eco-efficiency are focussed on manufacturing processes rather than on product design, since chemical composition and structure of the Roche pharmaceutical products are defined by the desired therapeutic effect, in contrast to commodities. Three examples of currently operating eco-efficient processes at Roche are described. They cover main areas for further improvement of both environmental performance and economical benefit: less material intensity and waste for disposal, energy recovery, minimization of water consumption. Furthermore, four different indicators currently used at Roche to track environmental performance and eco-efficiency are presented: the Roche Environmental Impact Figure (REIF), the Roche Energy Rate (RER), the Roche contribution to man-made global warming (CO2 equivalents), and the Eco-Efficiency Rate (EER). These key indicators are used as a basis to recognize weaknesses and strengths, to take decisions for improvement, to set environmental targets, and as management information.
Improvements in Waste Minimization, Process Safety, and Running Costs by Integrated Process Development
Authors: Morsey David , Nishioka Masato , Suter Georg , Stahala Peter
Published: April 2022

By the development of a new recycling process for spent acid in the manufacture of the 1-chloro-2,4-dinitrobenzene (CDNB) effective improvements in the waste balance and the process safety were achieved. Under the old process, the sulfuric acid generated could not be sold to the low
strength sulfuric-acid market, because it had a high concentration of organic contaminants. The resulting waste stream had long been a costly issue. A laboratory feasibility study followed by pilot evaluation qualified continuous extraction as an appropriate technology for purifying the acid.
With the change from a batch extraction process to a continuous extraction on a column, the quality of the acid could be improved such that use without further regeneration is possible now. Thus, the continuous extraction column offered improved efficiency, safety, and product consistency
as compared to the corresponding batch process.
Electrostatic Hazards in Powder Handling Operations
Authors: Glor Martin
Published: April 2022

Charge build-up is observed in most powder handling operations as soon as the powder is highly insulating or the equipment is made from highly insulating material. The ignition probability by discharges due to static electricity can drastically be reduce in practice, if only conductive
material is used for all parts of the equipment and installations and if all these parts are safely earthed. The question remains, however, whether the charge retained on a highly insulating product in powder form will be able to ignite this powder, even if the powder is handled and processed
in conductive and earthed equipment. Based on extensive research performed during the last decade in this field, ignition of highly insulating powder must be expected under certain circumstances (formation of so-called cone discharges), even if the powder is handled or processed in metallic
and earthed equipment.
Environmental Risk Assessment of Chemical Substances
Authors: Richner Peter , Weidenhaupt André
Published: April 2022

According to the OECD, it is estimated that some 70000 synthetic chemicals are in daily use. This number is still growing. Some of these products (e.g. polychlorinated biphenyls or chlorofluorocarbons) have gained great public attention due to their unexpected undesirable long-term impact on the ecosystem. The industrialized nations have therefore implemented and enforced stringent laws, in order to control the use of potentially harmful substances.It is an almost impossible task to have the EU Base Set available for all existing substances. The EU and other organizations like OECD have therefore put together priority lists of potentially harmful high-volume chemicals which are assessed by experts. The last couple of years, a tremendous amount of work has been done to develop computer-based modeling systems to predict the environmental behavior and distribution of chemical substances.There are models around (e.g. Mackay, USES, TGD EU, and others) to describe environmental distribution (Predicted Environmental Concentration (PEC)) of nonionic and nonpolar substances. For a first assessment, only a few physical properties (MP, BP, SOL, and possibly pKa) are needed. For ionic and/or polar substances, expert know-how is required.For environmental toxicity (Predicted No Effect Concentration (PNEC)), however, the situation is far more complex. There are different modes of action for each trophic level (algae, crustacea, fish). Computer models with Quantitative Structure-Activity Relationship (QSAR) offer a scientifically attractive tool to predict aquatic toxicity and biodegradation. There are no models that are applicable to heterogeneous chemical classes without expert know-how. Further progress can therefore be expected.The result of an ERA for perchloroethylene with USES is presented, and the problems of the adequacy of the model parameters explained. Here too, a further improvement is addressed.QSARs are attractive tools to design products with improved environmental compatibility at the research stage even before the first synthesis. In order to achieve such an ambitious aim, QSAR models that also include expert rules and evaluated results and their dependence on molecular structures will have to be further developed.
Stand der Sicherheitsvorschriften für Chemische Produkte in Europa
Authors: Bastian Claude , Eggimann Walter
Published: April 2022

Over the past 20 years an impressive number of environmental legislative instruments have been implemented across the ED, part of which have widely influenced the development, the production and the marketing of chemical substances and products. The need to align ecology and economy
in the marketplace under the approach of sustainable development has defined a policy designed to exert control on the handling of chemicals. Safe product use and environmental protection have become key activities with the objective to safeguard the environment, the workers as well as the
consumers when they get into contact with chemical products. In 1967 the so-called Dangerous Substances Directive has paved the way for providing a maximum of protection regarding the safe handling of chemicals while avoiding barriers to trade in the EU. Today the legislative developments
have evolved towards the risk assessment (and management) of new and existing chemicals. These instruments have been accompanied by an increasing need for information to be shared with various audiences, and of which the Safety Data Sheet represents probably the most largely distributed document.
The Biological Stability of β-Peptides: No Interactions between α- and β-Peptidic Structures?
Authors: Hintermann Tobias , Seebach Dieter
Published: April 2022

The use of peptides in pharmaceutical applications is always hindered by the rapid degradation of the peptides by enzymes. Recent work on β-peptides, peptides constructed entirely from β-amino acids, has shown that even the short-chain oligomers (6 or 7 residues) exhibit remarkably stable secondary structures. However, before certain applications of β-peptides can be considered, an information about their possible interactions or reactions with enzymes must be acquired.Ames tests (all negative) have now been performed on a selection of β-amino acids, which would be the result of the enzymatic degradation of a β-peptide. Furthermore, digestion experiments using a variety of peptidases and β-peptides have now shown that β-peptides, in sharp contrast to their α-peptide counterparts, undergo no degradation.
Selective Action of 4'-Benzoylated Thymidine on DNA Polymerases and Reverse Transcriptases
Authors: Marx Andreas , Giese Bernd
Published: April 2022

4'-Acylated thymidine triphosphates 1 have been synthesized and tested as substrates for DNA polymerases and reverse transcriptases. The 4'-benzoylated thymidine 1d was selectively acting as a chain terminator for the DNA synthesis catalyzed by retroviral RT. No incorporation of 1d was observed when DNA polymerases were used. The selective targeting of the action performed by retroviral enzymes is a requirement for an effective antiviral agent with a minimum of toxicity.
In memory of Oleg V. Kononov (1932–2021)
Authors: Граменицкий Е.Н.
Published: April 2022

некролог

necrologue
Large Piezoelectric Response in Ferroelectric/Multiferroelectric Metal Oxyhalides MOX2 (M = Ti, V and X = F, Cl and Br) Monolayers
Authors: Noor-A-Alam Mohammad , Nolan Michael
Published: April 2022

Flexible two-dimensional (2D) piezoelectric materials are promising for applications in wearable electromechanical nano-devices such as sensors, energy harvesters, and actuators. A large piezoresponse is required for any practical applications. Based on first-principles calculations, we report that ferroelectric TiOX2 as well as multiferroelectric VOX2 (X = F, Cl, Br) monolayers exhibit significantly large in-plane stress (e11) and strain (d11) piezoelectric coefficients. For example, in-plane piezo-response of TiOBr2 (both e11 and d11) is about an order of magnitude larger than that of widely studied 1H-MoS2 monolayer, and also quite comparable to giant piezoelectricity of group-IV monochalcogenide monolayers e.g., SnS. Moreover, d11 of MOX2 monolayers - ranging from 29.028 pm/V to 37.758 pm/V - are significantly higher than the d11 or d33 of commonly used 3D piezoelectrics such as w-AlN (d33 = 5.6 pm/V) and α-quartz (d11 = 2.27 pm/V). Such large d11 of MOX2 monolayers originates from low in-plane elastic constants with large e11due to large Born effective charges (Zij ) and atomic sensitivity ( du/dη ) to an applied strain. We also show the possibility of opening a new way of controlling piezoelectricity by magnetic field.
A Microporous Poly(arylene ether) Platform for Membrane-Based Gas Separation
Authors: Guo Sheng , Yeo Jing Ying , Benedetti Francesco , Syar Duha , Swager Timothy , Smith Zachary
Published: April 2022

Membrane-based gas separations are viewed as a critical component to accessing low-energy feedstocks and decarbonizing the chemical industry. However, it is exceedingly challenging to synthesize membrane materials that are high-performing, scalable, and processable. As a class of materials, microporous organic polymers (MOPs), which combine the gas sieving ability of microporous materials with the solution-processability of organic polymers, are highly desirable. Herein, we report the rational design and synthesis of linear microporous poly(arylene ether)s (PAEs) via Pd-catalyzed C-O polycondensation reaction. The scaffold of these microporous polymers consists of rigid three-dimensional triptycene and highly stereocontorted spirobifluorene, which endow these polymers with large internal free volume as well as high porosity with angstrom-sized pores. Unlike classic polymers of intrinsic microporosity (PIMs), this robust methodology for the synthesis of poly(arylene ether)s allows for the facile incorporation of functionalities and branched linkers for control of permeation and mechanical properties. CO2-philic groups, such as nitrile and tertiary amine groups, can be incorporated into this microporous polymeric scaffold for enhancing CO2 separation performance. In addition, a solution-processable branched polymer prepared using this synthetic strategy showed good gas separation performance and enhanced mechanical properties, which allowed for the formation of a submicron defect-free film with permeance-selectivity property sets that are comparable to high-performance ultrathin polymer membranes that have been optimized at industrial scale. In contrast with commercially available polymer membranes, the easily accessible PAE branching motif endows these materials with plasticization resistance. The structural tunability, high physical stability, and ease of processing suggest that this new platform of microporous polymers provides generalizable design strategies to address outstanding separation challenges for gas separation membranes.
Accurate calculation of absolute protein-ligand binding free energies
Authors: Chen Wei , Cui Di , Abel Robert , Friesner Richard A. , Wang Lingle
Published: April 2022

In the hit identification stage of drug discovery, a diverse chemical space needs to be explored to identify initial hits. Contrary to empirical scoring functions, absolute protein-ligand binding free energy perturbation (AB-FEP) provides a theoretically more rigorous and accurate description of protein ligand binding thermodynamics and could in principle greatly improve the hit rates in virtual screening. In this work, we describe an implementation of an accurate and reliable AB-FEP method in FEP+. We validated the AB-FEP method on eight congeneric compound series binding to eight protein receptors including both neutral and charged ligands. For ligands with net charges, the alchemical ion approach was adopted to avoid artifacts in electrostatic potential energy calculations. The calculated binding free energies were highly correlated with experimental results with the weighted average of R-square of 0.55 for the entire dataset and an overall RMSE of 1.1 kcal/mol when protein reorganization effect upon ligand binding was accounted for. Through AB-FEP calculations using apo versus holo protein structures, we demonstrated that the protein conformational and protonation state changes between the apo and holo proteins are the main physical factors contributing to the protein reorganization free energy manifested by the overestimation of raw AB-FEP calculated binding free energies using the holo structures of the proteins. The highly accurate AB-FEP results demonstrated in this work position it as a useful tool to improve the hit rates in virtual screening, thus facilitate hit discovery.
Emerging chemical heterogeneities in a commercial 18650 Li-ion battery during early cycling
Authors: Matras Dorota , Ashton Thomas E. , Dong Hongyang , Mirolo Marta , Martens Isaac , Drnec Jakub , Darr Jawwad A. , Quinn Paul D. , Jacques Simon D.M. , Beale Andrew M. , Vamvakeros Antonis
Published: April 2022

Synchrotron X-ray diffraction computed tomography (XRD-CT) was employed to study a commercial 18650 cylindrical LiNi0.8Co0.15Al0.5O2 (NCA) battery under operating conditions and during seven cycles. Multiple chemical heterogeneities related to the lithium distribution were observed in both the cathode and the anode from the analysis of the spatially-resolved diffraction signals. It is shown that during the battery charging, the anode exhibits different degrees of activity regarding the lithiation process. Explicitly, the following three regions were identified: uniform/homogenous lithiation, delayed lithiation and inactive-to-lithiation regions. The inactive-to-lithiation anode region was a result of the specific cell geometry (i.e. due to lack of cathode tape opposite these anode areas) and throughout the cycling experiments remained present in the form of LiC30-30+. The delayed lithiation region was seen to have a direct impact on the properties of NCA in its close proximity during the battery discharging, preventing its full lithiation. Further to this, the aluminum tab negatively affected the NCA in direct contact with it, leading to different lattice parameter a and c evolution compared to the rest of the cathode.
Peptidomimetic small-molecule inhibitors of 3CLPro activity and Spike-ACE2 interaction: towards dual-action molecules against Coronavirus infections
Authors: Tedesco Filomena , Calugi Lorenzo , Lenci Elena , Trabocchi Andrea
Published: April 2022

The development of molecules able to target protein-protein interactions (PPIs) is of interest for the development of nov-el therapeutic agents. Since a high percentage of PPIs are mediated by α-helical structure at the interacting surface, pep-tidomimetics that reproduce the essential conformational components of helices are useful templates for the develop-ment of PPIs inhibitors. In this work, the synthesis of a constrained dipeptide isostere and insertion in the short peptide epitope EDLFYQ of the ACE2 α-helix 1 domain resulted in the identification of a molecule capable of inhibiting the SARS-CoV-2 ACE-2/Spike interaction in the micromolar range. Moreover, inhibition of SARS-CoV-2 3CLPro main protease activi-ty was assessed as an additional inhibitory property of the synthesized peptidomimetics, taking advantage of the C-terminal Q amino acid present in both the ACE2 epitope and the Mpro recognising motif (APSTVxLQ), thus paving the way to the development of multitarget therapeutics towards Coronavirus infections.
Activating the potent antimicrobial activities of gold nanoclusters against multidrug resistant Pseudomonas aeruginosa
Authors: Ndugire William , Troung Dang , Raviranga N.G. Hasitha , Jingzhe Lao , Ramstrom Olof , Yan Mingdi
Published: April 2022

In this work we show that biological inactive gold nanoclusters (AuNCs) capped with D-maltose can be converted to antimicrobial AuI species by the addition of thiourea (TU). The antimicrobial activity mainly arises from the reaction of AuNCs with TU generating [Au(TU)2]Cl and small Au nanoclusters. Excess TU also maintains the oxidation state as AuI (vs. AuIII) which is key in maintaining activity. The AuNCs/TU combination was a powerful bactericidal agent against resistant bacteria, including multidrug-resistant (MDR) clinical isolates of Pseudomonas aeruginosa, and could eradicate S. epidermidis biofilm. It is unaffected by the efflux or bacterial outer membrane. The modes of action are multiple, including inhibition of thioredoxin reductase, CuI regulation interference and depletion of ATP. The formulation was 30-60 times less toxic on mammalian cells. This represents a new strategy enabling the antimicrobial activity of otherwise inactive AuNCs against the most difficult to treat MDR bacteria.
More is different: activating luminescence in aggregate via restriction of inter-molecular motion
Authors: deshuang tu , Hu Lianrui , Bian Xuhui , Zhang Yucui , Sung Herman H. Y. , Ryan KWOK Tsz Kin , Lam Jacky W. Y. , WILLIAMS Ian Duncan , han lei , Tang Ben Zhong
Published: April 2022

Molecular motion is related to the structures and properties of the molecules and their aggregates. Owing to both weak intermolecular interactions and complicated interplay between molecules, the manipulation of inter-molecular motion to realize specific structures and properties as well as applications, is challenging but attractive. Here, we reported that the photoluminescence property of luminogens could be tuned by the manipulation of the inter-molecular motion based on the dynamic ionic bond between the cation of acridinium and the anion of tetraphenyl boron. The free inter-molecular motion and the strong attraction of the ionic bond in the non/less polar solvents enabled the formation of a dark state in the excited state with faint emission. In contrast, multiple ionic bonds between cation and anion together with non-covalent interactions were observed in the crystalline state. This directly contributed to the restriction of the inter-molecular motion (RIMM), and eventually gave rise to bright aggregation-induced emission. Such a RIMM model for efficient solid-state emission can be validated by several organic ionic species. More importantly, this type of “multicomponent luminogens” showed remarkable reactive oxygen species generation, which enabled them to kill bacteria even superbugs upon white-light irradiation. This study not only provided fundamental insights into the molecular motion-structure-property relationship, but also opened up the possibility of constructing highly efficient luminogens in aggregates via RIMM for advanced applications.
Mechanical Bond Enhanced Lithium Halide Ion-Pair Binding by Halogen Bonding Heteroditopic Rotaxanes
Authors: Munasinghe Vihanga , Pancholi Jessica , Manawadu Dilhan , Zhang Zongyao , Beer Paul
Published: April 2022

A family of novel halogen bonding (XB) and hydrogen bonding (HB) heteroditopic [2]rotaxane host systems constructed by active metal template (AMT) methodology, were studied for their ability to cooperatively recognise lithium halide (LiX) ion-pairs. 1H NMR ion-pair titration experiments in CD3CN:CDCl3 solvent mixtures revealed a notable “switch-on“ of halide anion binding in the presence of a co-bound lithium cation, with rotaxane hosts demonstrating selectivity for LiBr over LiI. The strength of halide binding was shown to greatly increase with increasing number of halogen bond donors integrated into the interlocked cavity, where an all-XB rotaxane was found to be the most potent host for LiBr. DFT calculations corroborated these findings, determining the mode of LiX ion-pair binding. Notably, ion-pair binding was not observed with the corresponding XB/HB macrocycles alone, highlighting the cooperative heteroditopic rotaxane axle-macrocycle component mechanical bond effect as an efficient strategy for ion-pair recognition in general.
Synthesis and Optical Characterization of a Rhodamine B Spirolactam Dimer
Authors: Stratton Brandy-Fey , Pierre Angelina , Riser Elizabeth , Grinalds Nathan , Edwards Charles , Wohlwend Anna , Bauer Jacob , Spera Rachel , Pferdmenges Lauren , Griffith Kaitlyn , Hunter Brandon , Bobadova-Parvanova Petia , Day Cynthia , Lundin Pamela , Fogarty Keir
Published: April 2022

Amide derivatives of xanthene dyes such as rhodamine B are useful in a variety of sensing applications due to their colorimetric responses to stimuli such as acidity changes and UV light. The optical properties of these molecules can be influenced by intermolecular associations into dimeric structures, but the exact impact can be hard to predict. We have designed a covalently linked intramolecular dimer of the dye rhodamine B utilizing p-phenylene diamine to link the two dyes via amide bonds. The doubly closed spirolactam version of this dimer, RSL2, is isolated as a colorless solid. Under acidic conditions or UV exposure, RSL2 solutions develop a pink color that is expected for the ring-opened form of the molecule. However, NMR and single crystal diffraction data show that the equilibrium still prefers the closed dimer state. Interestingly, the emission profile of RSL2 shows solvatochromic blue fluorescence. Control studies of model compounds with similar structural motifs do not display similar blue fluorescence, indicating that this optical behavior is unique to the dimeric form. This behavior may lend itself to applications of such xanthene dimers to more sophisticated sensors beyond those with traditional binary on/off fluorescence profiles.
Surface Functionalization of Polypropylene Nonwoven Fabric for Introducing Repeatable Controlled Drug Release Property
Authors: Yamamoto Keita , Asahara Haruyasu , Moriguchi Maiko , Inoue Tsuyoshi
Published: April 2022

We developed polypropylene nonwoven fabrics (PP NWFs) with controlled drug release property via surface modification using the photo-activated chlorine dioxide radical (ClO2•) oxidation method, followed by β-cyclodextrin (CD) loading. PP materials are challenging to functionalize for allowing the immobilization of drugs, owing to their low reactivity and surface energy. Our β-CD/PP NWFs composite showed sustained drug release behavior over 12 h in phosphate buffer, indicating that β-CDs supported on PP fibers functioned successfully. Our functionalization method is desirable for drug delivery in medicinal chemistry.
Phosphine-Mediated Three-Component Bioconjugation of Amino- and Azidosaccharides in Ionic Liquids
Authors: Ohata Jun , Hall Yvonne , Uzoewulu Chiamaka , Nizam Zeinab , Ishizawa Seiya , El-Shaffey Hisham
Published: April 2022

Bioconjugation of carbohydrates has advanced the modern chemical biology and medical science research by incorporation of desired functionalities to the oxygen-rich biomolecules. However, the labeling process or selective chemical reaction of carbohydrates have been a challenging task because of their chemical, functional, and structural diversities, and no single chemical modification tool can be universally applicable to all the target substrates in different environments. In this report, we have developed a bioconjugation strategy for labeling of carbohydrate derivatives through a phosphine-mediated three-component coupling reaction in an ionic liquid medium. The multiple characterization methods identified a urea group as the reaction product of the phosphine-mediated coupling through the installation of carbonyl group from carbon dioxide in air and loss of nitrogen gas from the azide group. We have developed purification protocols to facilitate the cleanup and analysis of ionic liquid-based bioconjugation processes, which can be used for a diverse set of carbohydrate derivatives. The phosphine-mediated urea-forming reaction was applied to a variety of amine- and azide-containing carbohydrates such as antibiotics, anti-tumor agent, and polysaccharide with corresponding azide- and amine-based reagent, respectively. The ionic liquid-based bioconjugation was amenable for the chemical modification of the mammalian cell lysate in an azide-dependent manner. Thus, the present report represents not only the advancement of the nonaqueous bioconjugation method for carbohydrate derivatives from the reaction development perspectives, but also their practical utility for creation of carbohydrate conjugates as well as a study tool of the biomolecule through the bioorthogonal chemistry-like reactivity.
Generative Adversarial Neural Networks for Denoising Coherent Multidimensional Spectra
Authors: Al-Mualem Ziareena , Baiz Carlos
Published: April 2022

Ultrafast spectroscopy often involves measuring weak signals and long data acquisition times. Spectra are typically collected as a “pump-probe” spectrum by measuring differences in intensity across laser shots. Shot-to-shot intensity fluctuations are most often the primary source of noise in ultrafast spectroscopy. Here we present a novel approach for denoising ultrafast two-dimensional infrared (2D IR) spectra using conditional generative adversarial neural networks (cGANNs). The cGANN approach is able to eliminate shot-to-shot noise and reconstruct the lineshapes present in the noisy input spectrum. We present a general approach for training the cGANN using matched pairs of noisy and clean synthetic 2D IR spectra based on the Kubo-lineshape model for a three-level system. Experimental shot-to-shot laser noise is added to synthetic spectra to recreate the noise profile present in measured experimental spectra. The cGANNs can recover lineshapes from synthetic 2D IR spectra with signal-to-noise ratios as low as 2:1, while largely preserving the key features such as center frequencies, linewidths, and diagonal elongation. In addition, we benchmark the performance of the cGANN using experimental 2D IR spectra of an ester carbonyl vibrational probe and demonstrate that by applying the cGANN denoising approach, we can extract the frequency-frequency correlation function (FFCF) from reconstructed spectra using a nodal-line slope analysis. Finally, we provide a set of practical guidelines for extending the denoising method to other coherent multidimensional spectroscopies.
Dipole Switching by Intramolecular Electron Transfer in Single-Molecule Magnetic Complex [Mn12O12(O2CR)16(H2O)4]
Authors: Skachkov Dmitry , Liu Shuang-Long , Chen Jia , Christou George , Hebard Arthur , Zhang Xiao-Guang , Trickey Samuel , Cheng Hai-Ping
Published: April 2022

We study intramolecular electron transfer in the single-molecule magnetic complex [Mn12O12(O2CR)16 (H2O)4] for R = -H, -CH3, -CHCl2, -C6H5, -C6H4F ligands as a mechanism for switching of the molecular dipole moment. Energetics are obtained using the density functional theory (DFT) with onsite Coulomb energy correction (DFT+U). Lattice distortions are found to be critical for localizing an extra electron on one of the easy sites on the outer ring in which localized states can be stabilized. We find that the lowest energy path for charge transfer is for the electron to go through the center via superexchange mediated tunneling. The energy barrier for such a path ranges from 0.4 meV to 54 meV depending on the ligands and the isomeric form of the complex. The electric field needed to move the charge from one end to the other, thus reversing the dipole moment, is about 0.03 V/Å.
Mitigating the non-specific rolling circle amplification: a comprehensive assessment of the role of ligation and digestion methods
Authors: Nair Vandana Kuttappan , Sharma Chandrika , Ghosh Souradyuti
Published: April 2022

Rolling circle amplification (RCA) has been utilized for detecting a diverse range of analytes, molecular pathways, and in cellular imaging. However, non-specific amplification (NSA, amplification in absence of a target analyte) in RCA assays, especially those involving pre-synthesized circular DNA (cDNA), affects its sensitivity and specificity. NSA could originate from inefficient ligation or the succeeding cDNA purification steps. To quantify the NSA in RCA here, cDNA substrates were prepared using either self-annealing, splint-padlock, or cohesive end ligations. The cDNAs were then each subjected to nine different exonuclease digestion steps and quantified for NSA under both linear and hyperbranched RCA conditions. We investigated buffer composition, divalent ion concentration, single or dual enzyme digestion, overhang length in cohesive end ligation, and splint length in splint-padlock ligation. When applied in tandem, the conditions successfully mitigated the NSA end-fluorescence 30 – 100 fold while reducing the relative NSA (with respect to primer assisted RCA) to ~5%. Besides understanding the mechanistic origin of NSA, novel aspects of enzyme-substrate selectivity, buffer composition, and the role of divalent ions in enzyme activity were discovered. With increasing analytical applications, this study will help standardize NSA-free RCA assays involving pre-synthesized cDNA.
An Amorphous Teflate Doped Aluminium Chlorofluoride: A Solid Lewis Superacid for the Dehydrofluorination of Fluoroalkanes
Authors: Braun Thomas , Bui Minh , Hoffmann Kurt , Riedel Sebastian , Heinekamp Christian , Scheurell Kerstin , Scholz Gudrun , Stawski Tomasz , Emmerling Franziska
Published: April 2022

An anion doped aluminium chlorofluoride AlCl0.1F2.8(OTeF5)0.1 (ACF-teflate) was synthesized. The material contains pentafluoroorthotellurate (teflate) groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by 73 cm1, which is larger than the shift for SbF5. Remarkably, ACF-teflate catalyzes dehydrofluorination reactions of monofluoroalkanes to yield olefins in C6D6. In these cases, no Friedel-Crafts products were formed.
Intra OIC-Region Trade: Application of Gravity Model
Authors:   Ajman University, Ajman, United Arab Emirates, Hanif Muhammad
Published: April 2022

Purpose: This study analyses the international trade among members of the Organisation of Islamic Cooperation (OIC) and documents the significant contributing factors. Methodology: Our sample includes 49 OIC-members (located from Southeast Asia to South America). The extended gravity model of international trade is applied to identify the determinants of intra-OIC region trade on the recent five years data (2014-18), at the time research conducted. Exports are used as proxy for the international trade between a pair of trading partners. Findings: Evidence supports the application of the basic gravity model in explaining trade variations within the OIC region. GDP contributes positively while distancing negatively. Common language contributes positively to trade flows. Shared borders and Inflation (importer and exporter) turned insignificant. Trade volume among OIC member countries is less than potential. Recommendations: OIC economies need to focus on growth through the production of value-added commodities-leading to an increase in international trade. Furthermore, surplus capital within the region may be shifted to economies with scarce capital. Significance: To the best of author’s knowledge, this is the only effort to present a comprehensive analysis of international trade within the OIC region through the application of the gravity model in recent years.
Design & Pricing of Islamic Asset-Based S. ukuk¯ Strips: An Endeavour towards Financial Development
Authors:   Department of Islamic Studies, University of Okara, Okara, Pakistan, Haider Waqas Ali , Aqeeq Muhammad Arsalan ,   University of Newcastle, NSW, Australia, Ghaffar Abdul ,   Department of Islamic Studies, University of Okara, Okara, Pakistan, Sajid Ali ,   Karachi Institute of Economics and Technology, Karachi, Pakistan
Published: April 2022

Purpose: The efficiency of the Islamic Financial Industry suffers from a lack of liquidity instruments and shallow secondary markets. This paper reviews the financial intermediation theory and the complementary role of debt and money markets towards the broader goal of allocative efficiency, asset transformation, and diversification for the welfare of all economic agents. Separately Tradable Registered Interest & Principle (STRIPs), created by disintegrating coupon and principal payment to be traded as discount bonds, have been effectively employed in the west for liquidity management. This paper proposes a novel idea of ij¯arah s.uk¯uk STRIPS (ISS) that splits the payoffs of ij¯arah s.uk¯uk. Method: The design and pricing of ISS are modeled employing lease valuation, certainty equivalent (C.E.), and bootstrapping. Instead of the prevalent capital asset-pricing model, volatility of ij¯arah s.uk¯uk payoffs is modeled using certainty equivalents, which extend the analysis to micro-level investor utility function. Also, the viability of ISS design is substantiated by numerical illustrations. Findings: We found that the proposed ISS can serve as a short-term liquidity management instrument, facilitate price discovery and define the term structure in Islamic debt markets. For sovereign issues, ISS can enable efficient monetary policy transmission, market completeness, and public finances for the underdeveloped Muslim world. Significance: To the best of our knowledge, this is the first study proposing the ISS as a financial innovation. The ISS proposed in this study will be a valuable addition to the arsenal of Islamic Financial offerings - augmenting the financial deepening and development of Islamic Financial Markets.
Development and Validation of A New Islamic Work Ethics Scale for Healthcare Providers in Emergency Departments (EDIWES)
Authors:   Universiti Sultan Zainal Abidin, Kuala Terengganu, Malaysia, Al-Samdi Audai Naji , Amaran Safiya ,   Universiti Sultan Zainal Abidin, Kuala Terengganu, Malaysia, Tengku Mohammad Ariff ,   Universiti Sultan Zainal Abidin, Kuala Terengganu, Malaysia, Alown Bandar Ersan ,   Universiti Sultan Zainal Abidin, Kuala Terengganu, Malaysia
Published: April 2022

Purpose: Research on work ethics has acquired considerable scholars’ attention. Research on employees’ religion-oriented ethics, particularly Islamic Work Ethics (IWE), has remained relatively narrow in healthcare settings. This study aims to develop and validate a scale to measure Healthcare Providers (HCPs) IWE in Emergency Departments (EDs). Design/methodology/approach: This study was conducted on HCPs who work at EDs in Jordan. The scale goes through a series of validation processes, including content validity, face validity, and construct validity. This study employed exploratory factor analysis for construct validity and Cronbach’s alpha for reliability analysis. Findings: Exploratory factor analysis yielded 17 strong explanatory items on a three-dimension scale, namely obligation of HCP to their patients, obligation of supervisors to their subordinates and obligation of HCP to their colleagues. Conclusion: The findings of this study provide a valid and reliable scale that had a satisfactory psychometric property for measuring Healthcare Providers’ IWE in EDs.