bluuebunny/crossref_metadata_2025 huggingface dataset:
Prevalence of Diabetes Mellitus among Patients with Tuberculosis and Its Associated Factors in Sana’a, Yemen, 2021
Authors: Alturki Sumia , Al Amad Mohammed , Mahyoub Esam , Al Hanash Noora , Alhammadi Abdulbary
Published: June 2023

Diabetes mellitus (DM) is one of tuberculosis’ (TB) ending barriers. TB patients with DM are at a higher risk than non-diabetes patients to develop complication, relapse and die. In Yemen, information on TB–DM comorbidity is lacking. This study aimed to determine the prevalence and associated factors of diabetes among TB patients at the National Tuberculosis Center (NTC) in Sana’a. A facility-based cross-sectional study was conducted. All TB patients aged >15 years who attended the NTC from July to November 2021 were screened for DM. Socio-demographic and behavioral information were collected through face-to-face interviews using questionnaires. A total of 331 TB patients were enrolled, 53% were males, 58% aged <40 years, and 74% were newly diagnosed with TB. Overall, DM prevalence was 18%. Higher rates of DM were found among TB patients that were male (OR = 3.0; 95% CI; 1.4–6.7), ≥50 years of age (OR = 10.8; 95% CI; 4.3–27.3), and those with a family history of diabetes (OR = 3.4; 95% CI; 1.6–6.9). Almost one fifth of TB patients had DM. The early detection of DM through immediate screening after a TB diagnosis and periodically during the course of treatment is crucial for TB patients’ optimal care. Dual diagnostics for reducing the dual burden of TB–DM comorbidity is recommended.
Spatial Principles of Territories Selection for Priority Development of Agroforestry Complexes
Authors: Tubalov Alexey A.
Published: June 2023

The creation of protective forest plantations on agricultural land is a long-term and capital-intensive investment aimed at creating sustainable agroforest landscapes. The purpose of the ongoing scientific research was to identify areas and create protective plantings, which will bring maximum effects. The methodology for achieving this goal is based on cartographic methods. Modern means of geoinformation modeling of territories and remote data make it possible to identify and follow the components of landscapes to obtain their quantitative characteristics. The result of the work carried out is a cartographic model of the study area, which allows for the analysis of the sufficiency of the number of existing forest plantations to ensure a sustainable development of the territories. The theoretical basis for determining the sufficiency of the number of forest plantations is the idea of the optimal forest cover of the territories. A review and analysis of existing points of view on the issue of optimal forest cover made it possible to identify the minimum parameters of protective forest cover. For the region of research, it is equal to 3%. The actual average value of the indicator of protective forest cover, calculated on the basis of the area of the entire study area, is 0.8%. The search for factors that determine the high efficiency of agroforestry measures made it possible to perform a differentiated assessment of the need for agroforestry measures. The ability to identify priority sites for the creation of protective forest plantations in these areas will bring maximum effects. The main principles of the search for areas of priority development are taking into account the geomorphological features of the study area, as well as the differences in the forest-growing properties of soils. The range of protective forest cover values for six geomorphologically different parts of the study area is from 0.6% to 2.7%. An analysis of the mutual arrangement of protective forest plantations and soil contours made it possible to identify the localization of spatial areas. When planning the creation of new protective forest plantations, priority is given to the most fertile lands, the indicators of protective forest cover of which are minimal.
Impact of Climate Change on Alpine Phenology over the Qinghai–Tibet Plateau from 1981 to 2020
Authors: Chen Siyu , Chen Youjun , Xu Kailei , Zhang Jinlun
Published: June 2023

Climate change is a major driver of cyclical and seasonal changes in alpine phenology. This study investigated how climate change affects vegetation phenology’s spatial and temporal responses on the Qinghai–Tibet plateau (QTP) from 1981 to 2020. We used the daily two-band enhanced vegetation index (EVI2) at a 0.05° spatial resolution for 1981–2014, 16-day moderate resolution imaging spectroradiometer (MODIS) enhanced vegetation index data for 2000–2020 at 250 m spatial resolution, and climate records from 106 meteorological stations from 1981 to 2020 to construct linear regression models and Mann–Kendall point test to understand the changes on QTP vegetation in response to climate change. We found that the temperature in April, July, and September controls vegetation growth, and spring precipitation (p < 0.05) influences the length of the growing period, with a partial correlation coefficient of −0.69. Over the past 40 years, temperature and precipitation changes on the QTP have not shown abrupt shifts despite the increasingly warm and dry spring climate. We observed a meridional distribution trend in the correlation between precipitation and alpine vegetation greening, browning and the length of the growing period. In regions experiencing strong warming, vegetation growth was hindered by a lack of precipitation. We conclude that climatic factors alone cannot fully explain the changing trends in vegetation phenology across the QTP.
Sequential Bioprocess with Gluconobacter oxydans and Candida tropicalis for Gluconic Acid and Single-Cell Protein Production from Enzymatic Hydrolysate
Authors: Cheng Lu , Huang Rong , Ying Jiaxun , Fu Yixiu , Zhou Xin , Jiang Kankan
Published: June 2023

To meet the growing global demand for gluconic acid as a cement and concrete retarder, inexpensive and abundant lignocellulosic materials are regarded as the most suitable alternatives to starchy materials. However, their enzymatic hydrolysate contains not only glucose but also xylose, which negatively affects the performance of gluconic acid as a retarder. Notably, glucose is preferentially bio-oxidized into gluconic acid by Gluconobacter oxydans, but gluconic acid cannot be metabolized by Candida tropicalis. Given this, an artificially designed biological cascade process, respectively employing Gluconobacter oxydans and Candida tropicalis, was established to successfully carry out glucose conversion into gluconic acid, and xylose into a single-cell protein, using the enzymatic hydrolysate of corncobs as a feedstock. This sequential fermentation process produced 95.8 g/L gluconic acid and 9.0 g/L single-cell protein from one liter of the enzymatic hydrolysate that initially contained 98.1 g/L of glucose and 25.4 g/L of xylose. The mass-balance calculation showed that approximately 280 grams of gluconic acid and 27 grams of the single-cell protein could be harvested from 1000 grams of the corncob feedstock. The results suggest that the above-mentioned two-step bioconversion method is efficient in utilizing glucose and xylose from lignocellulosic hydrolysates.
Forest Degradation in the Southwest Brazilian Amazon: Impact on Tree Species of Economic Interest and Traditional Use
Authors: Costa Jessica Gomes , Fearnside Philip Martin , Oliveira Igor , Anderson Liana Oighenstein , de Aragão Luiz Eduardo Oliveira e Cruz , Almeida Marllus Rafael Negreiros , Clemente Francisco Salatiel , Nascimento Eric de Souza , Souza Geane da Conceição , Karlokoski Adriele , de Melo Antonio Willian Flores , de Araújo Edson Alves , Souza Rogério Oliveira , Graça Paulo Maurício Lima de Alencastro , da Silva Sonaira Souza
Published: June 2023

Amazonian biodiversity has been used for generations by human populations, especially by Indigenous peoples and traditional communities in their cultural, social and economic practices. However, forest degradation, driven by forest fires, has threatened the maintenance of these resources. This study examined the effects of recent forest fires on species with timber, non-timber and multiple-use potential in Brazil’s state of Acre. Forest inventories in five forest types were analyzed, identifying species with timber, non-timber and multiple-use potential based on a review of existing scientific articles, books and studies in the technical literature. The indicators of the effect of forest fires on species density were based on the mean and standard deviation of tree density and absolute abundance. We found that 25% of the tree individuals have potential for use by humans, 12.6% for timber, 10.7% non-timber and 1.4% have multiple-use potential. With the negative impact of fire, the reduction in timber, non-timber and multiple-use potential can range from 2 to 100%, depending on the vegetation type and especially on the recurrence of fire. However, even in forests that are degraded by fire, species that are useful to humans can be maintained to a certain degree and contribute to other environmental services, thus they must be preserved.
Consistent Antipredator Behavioral Responses among Populations of Red River Pupfish with Disparate Predator Communities
Authors: Anderson Cody M. , Wisenden Brian D. , Craig Cody A. , Stockwell Craig A.
Published: June 2023

Many desert fishes, which evolved in isolated aquatic “islands” with limited predation pressure, have been severely impacted by non-native predators. These impacts have been attributed to the evolutionary loss of antipredator competence, known as the predator naiveté hypothesis. Recent work provided support for this hypothesis for one desert fish species. We sought to examine the generality of the predator naiveté hypothesis by evaluating antipredator competence in five populations of Red River pupfish (Cyprinodon rubrofluviatilis), a species that occupies habitats that vary in the degree of isolation and levels of fish species richness. Fish were exposed to a conspecific chemical alarm cue released from damaged epidermal tissue as a general assay of antipredator response. We found that pupfish from all five populations exhibited antipredator behavior in response to the alarm cue, regardless of the exposure to predation risk. These data provide evidence that antipredator responses to alarm cues are conserved in Red River pupfish, even in populations isolated from piscivorous species.
Optimal Contest Design When Policing Damaging Behavior
Authors: Gilpatric Scott M. , Hong Ye
Published: June 2023

We consider the design of a contest in which the prize may motivate not only productive efforts, but also some damaging aggressive behavior by contestants. The organizer must choose prizes and an enforcement regime defined as a limit on how much aggressiveness will be tolerated and the probability of inspection. When the value of contestants’ output is low, it may be optimal to motivate much less effort than first best because the prize spread necessary to induce higher effort necessitates a high level of enforcement, which is not worth the cost. On the other hand, when the output value is sufficiently high, it becomes optimal to offer a high prize spread to motivate substantial but still below first-best effort, with costly enforcement then being employed to constrain damaging aggressive behavior. Additionally, a less accurate inspection technology is associated with a tighter limit on aggressive behavior, and “zero tolerance” can be optimal if the aggressive behavior has no value.
“Who’d Have Thought?”: Unravelling Ancestors’ Hidden Histories and Their Impact on Dharug Ngurra Presences, Places and People
Authors: Rey Jo Anne
Published: June 2023

As a means of opening the lid on transgenerational silencing—which was a survival strategy for thousands of Indigenous families against intended cultural genocide—while balancing the place of auto/biography in that journey, this paper focuses on the impact of Ancestors’ hidden histories and how the discovery of those histories drives complex identifications when woven with Presences, places, and people on Dharug Ngurra/Country. Using my own family’s recently uncovered early colonial Ancestral storying, histories that involve Dharug traditional custodian, African slave, and Anglo characters, some as First Fleet arrivals, the paper considers the place of auto/biography as a form of agency that brings past into presence, and which, in turn, opens opportunities to heal, decolonise, and transform Dharug and, more broadly, Indigenous communities, their knowledges, practices, and ontologies. When this activation involves most of the metropolis known as Sydney, Australia, we recognise its transformative potential to change non-Indigenous people’s perspectives. When we recognise auto/biography as a form of ‘truth-telling’, it allows a space to re-story relationality, both human and other-than-human, and restores Indigenous presence into Ngurra for biodiverse justice in a climate-changing world. Addressing these matters through poetic multimedia allows a place of safety between the pain and the healing.
Lipid-Associated GWAS Loci Predict Antiatherogenic Effects of Rosuvastatin in Patients with Coronary Artery Disease
Authors: Kononov Stanislav , Azarova Iuliia , Klyosova Elena , Bykanova Marina , Churnosov Mikhail , Solodilova Maria , Polonikov Alexey
Published: June 2023

We have shown that lipid-associated loci discovered by genome-wide association studies (GWAS) have pleiotropic effects on lipid metabolism, carotid intima-media thickness (CIMT), and CAD risk. Here, we investigated the impact of lipid-associated GWAS loci on the efficacy of rosuvastatin therapy in terms of changes in plasma lipid levels and CIMT. The study comprised 116 CAD patients with hypercholesterolemia. CIMT, total cholesterol (TC), low-density lipoprotein cholesterol (LDL-C), and triglycerides (TG) were measured at baseline and after 6 and 12 months of follow-up, respectively. Genotyping of fifteen lipid-associated GWAS loci was performed by the MassArray-4 System. Linear regression analysis adjusted for sex, age, body mass index, and rosuvastatin dose was used to estimate the phenotypic effects of polymorphisms, and p-values were calculated through adaptive permutation tests by the PLINK software, v1.9. Over one-year rosuvastatin therapy, a decrease in CIMT was linked to rs1689800, rs4846914, rs12328675, rs55730499, rs9987289, rs11220463, rs16942887, and rs881844 polymorphisms (Pperm < 0.05). TC change was associated with rs55730499, rs11220463, and rs6065906; LDL-C change was linked to the rs55730499, rs1689800, and rs16942887 polymorphisms; and TG change was linked to polymorphisms rs838880 and rs1883025 (Pperm < 0.05). In conclusion, polymorphisms rs1689800, rs55730499, rs11220463, and rs16942887 were found to be predictive markers for multiple antiatherogenic effects of rosuvastatin in CAD patients.
Reproductive Behavior of Trialeurodes vaporariorum (Westwood) (Hemiptera: Aleyrodidae) Relative to Different Host Plants in an Intensive Tomato Crop Region of Chile
Authors: Albornoz Marta V. , Flores M. Fernanda , Calderón Edgardo , Bahamondes Sergio A. , Verdugo Jaime A.
Published: June 2023

Trialeurodes vaporariorum Westwood (Hemiptera: Aleyrodidae) is an important economic pest and has a worldwide distribution. In Chile, this species has been reported over a large geographical area and is associated with tomato production. Although several plants have been described as hosts of the whitefly, this insect’s behavior against multiple hosts is still unclear. Therefore, the objective of our work was to identify the host plants, behaviors, preferences, performance, and choices of T. vaporariorum. First, over one year, we monitored nine production sites where tomato is the principal crop and identified 50 host plants belonging to 27 families, mostly Asteraceae and Solanaceae. Among the plants, those that were most infested by greenhouse whiteflies comprised Solanum lycopersicum, Phaseolus vulgaris, Cucurbita maxima, Malva sylvestris, Bidens aurea, and Sonchus oleraceus. In laboratory tests, greenhouse whiteflies showed a greater preference for S. oleraceus, S. lycopersicum, and P. vulgaris. The highest population growth rate was observed for B. aurea, followed by S. lycopersicum and S. oleraceus. Significant differences were found in the pairwise choice test, showing a greater preference for C. maxima and S. lycopersicum. Although this pest tends to choose tomatoes, this crop was not always the first choice in terms of preference and performance. This information is necessary for the development of integrated whitefly management programs that include adjacent habitats.
An In Vitro Comparison of Elastoplastic and Viscoelastic Behavior of Dental Composites with Reversible Addition–Fragmentation Chain Transfer-Mediated Polymerization
Authors: Ilie Nicoleta
Published: June 2023

Reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization has been implemented in commercially available bulk-fill dental composites, with the idea of either optimizing polymerization at depth, while providing sufficient opacity, or reducing exposure time. The elastoplastic and viscoelastic behavior of the materials pursuing both ideas are described comparatively in connection with the microstructure of the materials and artificial aging. A 3-point bending test was followed by reliability and fractographical analyses. The elastoplastic and viscoelastic behavior was monitored with an instrumented indentation test equipped with a DMA-module at various frequencies (0.5–5 Hz). Data reveal that the similarity in filler loading is reflected in similar elastic moduli. Increased strength was offset by higher plasticity and creep and was related to microstructure. Aging showed a significantly stronger influence on material behavior than differences in composition. The elastoplastic parameters of both materials deteriorate as a result of aging, but to a material-specific extent. Aging has a strong influence on elastic material behavior, but very little on viscous material behavior. The parameter that is most sensitive to aging is damping behavior. Detailed laboratory characterization indicates comparable in vitro behavior with clinically successful materials.
Denial-of-Service Attack Defense Strategy for Continuous Variable Quantum Key Distribution via Deep Learning
Authors: Yin Wenhao , Zhou Yuhan , Huang Duan
Published: June 2023

In the practical Continuous Variable Quantum Key Distribution (CVQKD) system, there is a large gap between the ideal theoretical model and the actual physical system. There are still some inevitable flaws, which give quantum hackers the opportunity to manipulate the channel in complex communication environments and launch Denial of Service attacks on the quantum channel. Therefore, a DoS attack-aware defense scheme for the CVQKD system based on convolutional neural networks (CNN) is proposed. The simulation results show that the proposed model can effectively detect DoS attacks launched by quantum hackers in CVQKD system in a complex communication environment, and the model has strong robustness due to the addition of the attention mechanism module. In addition, multiple sets of comparative experiments show that compared with the existing artificial neural network model, the CNN-based model has higher accuracy and stability.
Predictors of Short-Term Mortality in Patients with Ischemic Stroke
Authors: Iluţ Silvina , Vesa Ştefan Cristian , Văcăraș Vitalie , Mureșanu Dafin-Fior
Published: June 2023

Background and Objectives: The purpose of this study is to investigate the predictive factors for intrahospital mortality in ischemic stroke patients. We will examine the association between a range of clinical and demographic factors and intrahospital mortality, including age, sex, comorbidities, laboratory values, and medication use. Materials and Methods: This retrospective, longitudinal, analytic, observational cohort study included 243 patients over 18 years old with a new ischemic stroke diagnosis who were hospitalized in Cluj-Napoca Emergency County Hospital. Data collected included the patient demographics, baseline characteristics at hospital admission, medication use, carotid artery Doppler ultrasound, as well as cardiology exam, and intrahospital death. Results: Multivariate logistic regression was used to determine which variables were independently associated with intrahospital death. An NIHSS score > 9 (OR—17.4; p < 0.001) and a lesion volume > 22.3 mL (OR—5.8; p = 0.003) were found to be associated with the highest risk of death. In contrast antiplatelet treatment (OR—0.349; p = 0.04) was associated with lower mortality rates. Conclusions: Our study identified a high NIHSS score and large lesion volume as independent risk factors for intrahospital mortality in ischemic stroke patients. Antiplatelet therapy was associated with lower mortality rates. Further studies are needed to explore the potential mechanisms underlying these associations and to develop targeted interventions to improve patient outcomes.
Improving the Energy Storage of Supercapattery Devices through Electrolyte Optimization for Mg(NbAgS)x(SO4)y Electrode Materials
Authors: Hassan Haseebul , Iqbal Muhammad Waqas , Alharthi Sarah , Amin Mohammed A. , Afzal Amir Muhammad , Ryl Jacek , Ansari Mohd Zahid
Published: June 2023

Electrolytes are one of the most influential aspects determining the efficiency of electrochemical supercapacitors. Therefore, in this paper, we investigate the effect of introducing co-solvents of ester into ethylene carbonate (EC). The use of ester co-solvents in ethylene carbonate (EC) as an electrolyte for supercapacitors improves conductivity, electrochemical properties, and stability, allowing greater energy storage capacity and increased device durability. We synthesized extremely thin nanosheets of niobium silver sulfide using a hydrothermal process and mixed them with magnesium sulfate in different wt% ratios to produce Mg(NbAgS)x)(SO4)y. The synergistic effect of MgSO4 and NbS2 increased the storage capacity and energy density of the supercapattery. Multivalent ion storage in Mg(NbAgS)x(SO4)y enables the storage of a number of ions. The Mg(NbAgS)x)(SO4)y was directly deposited on a nickel foam substrate using a simple and innovative electrodeposition approach. The synthesized silver Mg(NbAgS)x)(SO4)y provided a maximum specific capacity of 2087 C/g at 2.0 A/g current density because of its substantial electrochemically active surface area and linked nanosheet channels which aid in ion transportation. The supercapattery was designed with Mg(NbAgS)x)(SO4)y and activated carbon (AC) achieved a high energy density of 79 Wh/kg in addition to its high power density of 420 W/kg. The supercapattery (Mg(NbAgS)x)(SO4)y//AC) was subjected to 15,000 consecutive cycles. The Coulombic efficiency of the device was 81% after 15,000 consecutive cycles while retaining a 78% capacity retention. This study reveals that the use of this novel electrode material (Mg(NbAgS)x(SO4)y) in ester-based electrolytes has great potential in supercapattery applications.
Recent Advances in Synthetic Drugs and Natural Actives Interacting with OAT3
Authors: Chen Ying , Li Hongyan , Wang Ke , Wang Yousheng
Published: June 2023

Organic anion transporter 3 (OAT3) is predominantly expressed in the kidney and plays a vital role in drug clearance. Consequently, co-ingestion of two OAT3 substrates may alter the pharmacokinetics of the substrate. This review summarizes drug–drug interactions (DDIs) and herbal–drug interactions (HDIs) mediated by OAT3, and inhibitors of OAT3 in natural active compounds in the past decade. This provides a valuable reference for the combined use of substrate drugs/herbs for OAT3 in clinical practice in the future and for the screening of OAT3 inhibitors to avoid harmful interactions.
Mechanisms of Sulfoxidation and Epoxidation Mediated by Iron(III)-Iodosylbenzene Adduct: Electron-Transfer vs. Oxygen-Transfer Mechanism
Authors: Török Patrik , Lakk-Bogáth Dóra , Kaizer József
Published: June 2023

The mechanisms of sulfoxidation and epoxidation mediated by previously synthesized and characterized iron(III)-iodosylbenzene adduct, FeIII(OIPh) were investigated using para-substituted thioanisole and styrene derivatives as model substrates. Based on detailed kinetic reaction experiments, including the linear free-energy relationships between the relative reaction rates (logkrel) and the σp (4R-PhSMe) with ρ = −0.65 (catalytic) and ρ = −1.13 (stoichiometric), we obtained strong evidence that the stoichiometric and catalytic oxidation of thioanisoles mediated by FeIII(OIPh) species involves direct oxygen transfer. The small negative slope −2.18 from log kobs versus Eox for 4R-PhSMe gives further clear evidence for the direct oxygen atom transfer mechanism. On the contrary, with the linear free-energy relationships between the relative reaction rates (logkrel) and total substituent effect (TE, 4R-PhCHCH2) parameters with slope = 0.33 (catalytic) and 2.02 (stoichiometric), the stoichiometric and catalytic epoxidation of styrenes takes place through a nonconcerted electron transfer (ET) mechanism, including the formation of the radicaloid benzylic radical intermediate in the rate-determining step. On the basis of mechanistic studies, we came to the conclusion that the title iron(III)-iodosylbenzene complex is able to oxygenate sulfides and alkenes before it is transformed into the oxo-iron form by cleavage of the O−I bond.
Photocatalytic Transformation of Biomass and Biomass Derived Compounds—Application to Organic Synthesis
Authors: Gómez Fernández Mario Andrés , Hoffmann Norbert
Published: June 2023

Biomass and biomass-derived compounds have become an important alternative feedstock for chemical industry. They may replace fossil feedstocks such as mineral oil and related platform chemicals. These compounds may also be transformed conveniently into new innovative products for the medicinal or the agrochemical domain. The production of cosmetics or surfactants as well as materials for different applications are examples for other domains where new platform chemicals obtained from biomass can be used. Photochemical and especially photocatalytic reactions have recently been recognized as being important tools of organic chemistry as they make compounds or compound families available that cannot be or are difficultly synthesized with conventional methods of organic synthesis. The present review gives a short overview with selected examples on photocatalytic reactions of biopolymers, carbohydrates, fatty acids and some biomass-derived platform chemicals such as furans or levoglucosenone. In this article, the focus is on application to organic synthesis.
Analytical Quality by Design-Compliant Development of a Cyclodextrin-Modified Micellar ElectroKinetic Chromatography Method for the Determination of Trimecaine and Its Impurities
Authors: Marzullo Luca , Gotti Roberto , Orlandini Serena , Slavíčková Patricie , Jireš Jakub , Zapadlo Michal , Douša Michal , Nekvapilová Pavla , Řezanka Pavel , Furlanetto Sandra
Published: June 2023

In 2022, the International Council for Harmonisation released draft guidelines Q2(R2) and Q14, intending to specify the development and validation activities that should be carried out during the lifespan of an analytical technique addressed to assess the quality of medicinal products. In the present study, these recommendations were implemented in Capillary Electrophoresis method development for the quality control of a drug product containing trimecaine, by applying Analytical Quality by Design. According to the Analytical Target Profile, the procedure should be able to simultaneously quantify trimecaine and its four impurities, with specified analytical performances. The selected operative mode was Micellar ElectroKinetic Chromatography employing sodium dodecyl sulfate micelles supplemented with dimethyl-β-cyclodextrin, in a phosphate-borate buffer. The Knowledge Space was investigated through a screening matrix encompassing the composition of the background electrolyte and the instrumental settings. The Critical Method Attributes were identified as analysis time, efficiency, and critical resolution values. Response Surface Methodology and Monte Carlo Simulations allowed the definition of the Method Operable Design Region: 21–26 mM phosphate-borate buffer pH 9.50–9.77; 65.0 mM sodium dodecyl sulfate; 0.25–1.29% v/v n-butanol; 21–26 mM dimethyl-β-cyclodextrin; temperature, 22 °C; voltage, 23–29 kV. The method was validated and applied to ampoules drug products.
Hexahexyloxycalix[6]arene, a Conformationally Adaptive Host for the Complexation of Linear and Branched Alkylammonium Guests
Authors: Iuliano Veronica , Talotta Carmen , Della Sala Paolo , De Rosa Margherita , Soriente Annunziata , Neri Placido , Gaeta Carmine
Published: June 2023

Hexahexyloxycalix[6]arene 2b leads to the endo-cavity complexation of linear and branched alkylammonium guests showing a conformational adaptive behavior in CDCl3 solution. Linear n-pentylammonium guest 6a+ induces the cone conformation of 2b at the expense of the 1,2,3-alternate, which is the most abundant conformer of 2b in the absence of a guest. In a different way, branched alkylammonium guests, such as tert-butylammonium 6b+ and isopropylammonium 6c+, select the 1,2,3-alternate as the favored 2b conformation (6b+/6c+⊂2b1,2,3-alt), but other complexes in which 2b adopts different conformations, namely, 6b+/6c+⊂2bcone, 6b+/6c+⊂2bpaco, and 6b+/6c+⊂2b1,2-alt, have also been revealed. Binding constant values determined via NMR experiments indicated that the 1,2,3-alternate was the best-fitting 2b conformation for the complexation of branched alkylammonium guests, followed by cone > paco > 1,2-alt. Our NCI and NBO calculations suggest that the H-bonding interactions (+N–H···O) between the ammonium group of the guest and the oxygen atoms of calixarene 2b are the main determinants of the stability order of the four complexes. These interactions are weakened by increasing the guest steric encumbrance, thus leading to a lower binding affinity. Two stabilizing H-bonds are possible with the 1,2,3-alt- and cone-2b conformations, whereas only one H-bond is possible with the other paco- and 1,2-alt-2b stereoisomers.
Selective C–H Bond Cleavage with a High-Spin FeIV–Oxido Complex
Authors: Sun Chen , Jaimes Jennifer L. , Follmer Alec H. , Ziller Joseph W. , Borovik Andrew S.
Published: June 2023

Non-heme Fe monooxygenases activate C–H bonds using intermediates with high-spin FeIV–oxido centers. To mimic these sites, a new tripodal ligand [pop]3− was prepared that contains three phosphoryl amido groups that are capable of stabilizing metal centers in high oxidation states. The ligand was used to generate [FeIVpop(O)]−, a new FeIV–oxido complex with an S = 2 spin ground state. Spectroscopic measurements, which included low-temperature absorption and electron paramagnetic resonance spectroscopy, supported the assignment of a high-spin FeIV center. The complex showed reactivity with benzyl alcohol as the external substrate but not with related compounds (e.g., ethyl benzene and benzyl methyl ether), suggesting the possibility that hydrogen bonding interaction(s) between the substrate and [FeIVpop(O)]− was necessary for reactivity. These results exemplify the potential role of the secondary coordination sphere in metal-mediated processes.
Machine Learning Electron Density Prediction Using Weighted Smooth Overlap of Atomic Positions
Authors: Achar Siddarth K. , Bernasconi Leonardo , Johnson J. Karl
Published: June 2023

Having access to accurate electron densities in chemical systems, especially for dynamical systems involving chemical reactions, ion transport, and other charge transfer processes, is crucial for numerous applications in materials chemistry. Traditional methods for computationally predicting electron density data for such systems include quantum mechanical (QM) techniques, such as density functional theory. However, poor scaling of these QM methods restricts their use to relatively small system sizes and short dynamic time scales. To overcome this limitation, we have developed a deep neural network machine learning formalism, which we call deep charge density prediction (DeepCDP), for predicting charge densities by only using atomic positions for molecules and condensed phase (periodic) systems. Our method uses the weighted smooth overlap of atomic positions to fingerprint environments on a grid-point basis and map it to electron density data generated from QM simulations. We trained models for bulk systems of copper, LiF, and silicon; for a molecular system, water; and for two-dimensional charged and uncharged systems, hydroxyl-functionalized graphane, with and without an added proton. We showed that DeepCDP achieves prediction R2 values greater than 0.99 and mean squared error values on the order of 10−5e2 Å−6 for most systems. DeepCDP scales linearly with system size, is highly parallelizable, and is capable of accurately predicting the excess charge in protonated hydroxyl-functionalized graphane. We demonstrate how DeepCDP can be used to accurately track the location of charges (protons) by computing electron densities at a few selected grid points in the materials, thus significantly reducing the computational cost. We also show that our models can be transferable, allowing prediction of electron densities for systems on which it has not been trained but that contain a subset of atomic species on which it has been trained. Our approach can be used to develop models that span different chemical systems and train them for the study of large-scale charge transport and chemical reactions.
Super-Ballistic Width Dependence of Thermal Conductivity in Graphite Nanoribbons and Microribbons
Authors: Huang Xin , Masubuchi Satoru , Watanabe Kenji , Taniguchi Takashi , Machida Tomoki , Nomura Masahiro
Published: June 2023

The super-ballistic temperature dependence of thermal conductivity, facilitated by collective phonons, has been widely studied. It has been claimed to be unambiguous evidence for hydrodynamic phonon transport in solids. Alternatively, hydrodynamic thermal conduction is predicted to be as strongly dependent on the width of the structure as is fluid flow, while its direct demonstration remains an unexplored challenge. In this work, we experimentally measured thermal conductivity in several graphite ribbon structures with different widths, from 300 nm to 1.2 µm, and studied its width dependence in a wide temperature range of 10–300 K. We observed enhanced width dependence of the thermal conductivity in the hydrodynamic window of 75 K compared to that in the ballistic limit, which provides indispensable evidence for phonon hydrodynamic transport from the perspective of peculiar width dependence. This will help to find the missing piece to complete the puzzle of phonon hydrodynamics, and guide future attempts at efficient heat dissipation in advanced electronic devices.
Palladium Catalyzed Allylic C-H Oxidation Enabled by Bicyclic Sulfoxide Ligands
Authors: Wen Yuming , Zheng Jianfeng , Evans Alex H. , Zhang Qiang
Published: June 2023

The activation of C-H bonds is a potent tool for modifying molecular structures in chemistry. This article details the steps involved in a novel ligand bearing a bicyclic [3.3.1]-nonane framework and bissulfoxide moiety. A palladium catalyzed allylic C-H oxidation method enables a direct benzyl-allylic functionalization with the bissulfoxide ligand. Bissulfoixde ligand possesses a rapidly constructed bicyclic [3.3.1] framework and it proved to be effective for enabling both N- and C-alkylation. A total of 13 C-H activation productions were reported with good to excellent yields. This report validated that it is necessary to include bissulfoxide as a ligand for superior reactivities. Naftifine was produced utilizing developed C-H functionalization methodology in good overall yields.
Design of Tailor-Made Biopolymer-Based Capsules for Biological Application by Combining Porous Particles and Polysaccharide Assembly
Authors: Chesneau Cléa , Larue Laura , Belbekhouche Sabrina
Published: June 2023

Various approaches have been described in the literature to demonstrate the possibility of designing biopolymer particles with well-defined characteristics, such as size, chemical composition or mechanical properties. From a biological point of view, the properties of particle have been related to their biodistribution and bioavailability. Among the reported core–shell nanoparticles, biopolymer-based capsules can be used as a versatile platform for drug delivery purposes. Among the known biopolymers, the present review focuses on polysaccharide-based capsules. We only report on biopolyelectrolyte capsules fabricated by combining porous particles as a template and using the layer-by-layer technique. The review focuses on the major steps of the capsule design, i.e., the fabrication and subsequent use of the sacrificial porous template, multilayer coating with polysaccharides, the removal of the porous template to obtain the capsules, capsule characterisation and the application of capsules in the biomedical field. In the last part, selected examples are presented to evidence the major benefits of using polysaccharide-based capsules for biological purposes.
The Upper Nasal Space: Option for Systemic Drug Delivery, Mucosal Vaccines and “Nose-to-Brain”
Authors: Shrewsbury Stephen B.
Published: June 2023

Sino-nasal disease is appropriately treated with topical treatment, where the nasal mucosa acts as a barrier to systemic absorption. Non-invasive nasal delivery of drugs has produced some small molecule products with good bioavailability. With the recent COVID pandemic and the need for nasal mucosal immunity becoming more appreciated, more interest has become focused on the nasal cavity for vaccine delivery. In parallel, it has been recognized that drug delivery to different parts of the nose can have different results and for “nose-to-brain” delivery, deposition on the olfactory epithelium of the upper nasal space is desirable. Here the non-motile cilia and reduced mucociliary clearance lead to longer residence time that permits enhanced absorption, either into the systemic circulation or directly into the CNS. Many of the developments in nasal delivery have been to add bioadhesives and absorption/permeation enhancers, creating more complicated formulations and development pathways, but other projects have shown that the delivery device itself may allow more differential targeting of the upper nasal space without these additions and that could allow faster and more efficient programs to bring a wider range of drugs—and vaccines—to market.
Method and Installation for Efficient Automatic Defect Inspection of Manufactured Paper Bowls
Authors: Yu Shaoyong , Lee Yang-Han , Chen Cheng-Wen , Gao Peng , Xu Zhigang , Chen Shunyi , Yang Cheng-Fu
Published: June 2023

Various techniques were combined to optimize an optical inspection system designed to automatically inspect defects in manufactured paper bowls. A self-assembled system was utilized to capture images of defects on the bowls. The system employed an image sensor with a multi-pixel array that combined a complementary metal-oxide semiconductor and a photo detector. A combined ring light served as the light source, while an infrared (IR) LED matrix panel was used to provide constant IR light to highlight the outer edges of the objects being inspected. The techniques employed in this study to enhance defect inspections on produced paper bowls included Gaussian filtering, Sobel operators, binarization, and connected components. Captured images were processed using these technologies. Once the non-contact inspection system’s machine vision method was completed, defects on the produced paper bowls were inspected using the system developed in this study. Three inspection methods were used in this study: internal inspection, external inspection, and bottom inspection. All three methods were able to inspect surface features of produced paper bowls, including dirt, burrs, holes, and uneven thickness. The results of our study showed that the average time required for machine vision inspections of each paper bowl was significantly less than the time required for manual inspection. Therefore, the investigated machine vision system is an efficient method for inspecting defects in fabricated paper bowls.
Structural, Optical, and Electrical Parameters of Doped PVA/PVP Blend with TPAI or THAI Salt
Authors: El-Naggar A. M. , Brnawi Shadia Z. , Kamal A. M. , Albassam A. A. , Heiba Zein K. , Mohamed Mohamed Bakr
Published: June 2023

The 70% polyvinyl alcohol/30% polyvinyl pyrrolidone (PVA/PVP) polymer blends, with different weight ratios of tetrapropylammonium iodide (TPAI) or tetrahexylammonium iodide (THAI) salt, were prepared using dimethyl sulfoxide (DMSO) as a solvent. The X-ray diffraction technique was used to trace the crystalline nature of the formed blends. The SEM and EDS techniques were applied to figure out the morphology of the blends. The variation in the FTIR vibrational bands was used to investigate the chemical composition and the effect of different salt doping on the functional groups of the host blend. The influence of the salt type (TPAI or THAI) and its ratio on the linear and nonlinear optical parameters for the doped blends were investigated in detail. Absorbance and reflectance are highly enhanced in the UV region reaching a maximum for the blend with 24% TPAI or THAI; so, it can be employed as shielding materials for UVA and UVB types. The direct (5.1 eV) and indirect (4.8 eV) optical bandgaps were reduced continuously to (3.52, 3.63 eV) and (3.45, 3.51 eV) while increasing the content of TPAI or THAI, respectively. The blend doped with 24% wt TPAI exhibited the highest refractive index (around 3.5 in 400–800 nm). The DC conductivity is affected by the content and type of salt, its dispersion, and blend-salt interaction. The activation energies of different blends were obtained by applying the Arrhenius formula.
Degradation and Lifetime Prediction of Epoxy Composite Insulation Materials under High Relative Humidity
Authors: Ma Jielin , Yang Yan , Wang Qi , Deng Yuheng , Yap Malvern , Chern Wen Kwang , Oh Joo Tien , Chen Zhong
Published: June 2023

Insulation failure of composite epoxy insulation materials in distribution switchgear under the stress of heat and humidity is one of the leading causes of damage to switchgear components. This work prepared composite epoxy insulation materials by casting and curing a diglycidyl ether of bisphenol A (DGEBA)/anhydride/wollastonite composite system, and performed material accelerated aging experiments under three conditions: 75 °C and 95% relative humidity (RH), 85 °C and 95% RH, and 95 °C and 95% RH. Material, mechanical, thermal, chemical, and microstructural properties were investigated. Based on the IEC 60216-2 standard and our data, tensile strength and ester carbonyl bond (C=O) absorption in infrared spectra were chosen as failure criteria. At the failure points, the ester C=O absorption decreased to ~28% and the tensile strength decreased to 50%. Accordingly, a lifetime prediction model was established to estimate material lifetime at 25 °C and 95% RH to be 33.16 years. The material degradation mechanism was attributed to the hydrolysis of epoxy resin ester bonds into organic acids and alcohols under heat and humidity stresses. Organic acids reacted with calcium ions (Ca2+) of fillers to form carboxylate, which destroyed the resin-filler interface, resulting in a hydrophilic surface and a decrease in mechanical strength.
Teleportation Revealed
Authors: Bédard Charles
Published: June 2023

Quantum teleportation is the name of a problem: How can the real-valued parameters encoding the state at Alice’s location make their way to Bob’s location via shared entanglement and only two bits of classical communication? Without an explanation, teleportation appears to be a conjuring trick. Investigating the phenomenon with Schrödinger states and reduced density matrices shall always leave loose ends because they are not local and complete descriptions of quantum systems. Upon demonstrating that the Heisenberg picture admits a local and complete description, Deutsch and Hayden rendered its explanatory power manifest by revealing the trick behind teleportation, namely, by providing an entirely local account. Their analysis is re-exposed and further developed.
Vitamin D Supplementation Impacts Calcium and Phosphorus Metabolism in Piglets Fed a Diet Contaminated with Deoxynivalenol and Challenged with Lipopolysaccharides
Authors: Sauvé Béatrice , Chorfi Younes , Montminy Marie-Pierre Létourneau , Guay Frédéric
Published: June 2023

Using alternative feed ingredients in pig diets can lead to deoxynivalenol (DON) contamination. DON has been shown to induce anorexia, inflammation, and—more recently—alterations in the vitamin D, calcium, and phosphorus metabolisms. Adding vitamin D supplementation in the form of vitamin D3 and 25-OH-D3 to the feed could modify the effects of DON in piglets. In this study, vitamin D3 or 25-OH-D3 supplementation was used in a control or DON-contaminated treatment. A repetitive exposure over 21 days to DON in the piglets led to disruptions in the vitamin D, calcium, and phosphorus metabolisms, resulting in a decreased growth performance, increased bone mineralization, and the downregulation of genes related to calcium and to phosphorus intestinal and renal absorption. The DON challenge also decreased blood concentrations of 25-OH-D3, 1,25-(OH)2-D3, and phosphate. The DON contamination likely decreased the piglets’ vitamin D status indirectly by modifying the calcium metabolism response. Vitamin D supplementations did not restore vitamin D status or bone mineralization. After a lipopolysaccharide-induced inflammatory stimulation, feeding a 25-OH-D3 supplementation increased 25-OH-D3 concentration and 1,25-(OH)2-D3 regulations during the DON challenge. DON contamination likely induced a Ca afflux by altering the intestinal barrier, which resulted in hypercalcemia and hypovitaminosis D. The vitamin D supplementation could increase the calcitriol production to face the combined LPS and DON challenge.
An Improved Model for Water Quality Management Accounting for the Spatiotemporal Benthic Flux Rate
Authors: Kim Semin , Park Youngki
Published: June 2023

Although water quality models provide useful interpretations for water quality management, it is critical to accurately input and simulate the flux rate, which varies with space and time. In the Environmental Fluid Dynamics Code model, the flux rate value set does not consider spatiotemporal variability. The water quality of the Saemangeum freshwater lake in Korea is poor despite quality improvement measures. In this study, the model was improved by considering the characteristics of flux rates that change spatiotemporally based on environmental conditions and factors influencing the benthic layer. An exponential relational expression was generated and applied to the model while considering the aerobic, anaerobic, and influencing factors. Results from four important sites in the Saemangeum Reservoir were compared with the RSR, %Difference, and AME results of the previous model for evaluating the reproducibility of the improved model. Calibration and verification of the model were performed in 2013 and 2016, respectively. The improved model yielded values close to the optimal value after computing the evaluation functions of both models. It had excellent reproducibility and simulated water quality by reflecting a reasonable value for the benthic flux rate. The improved model can be extended to evaluate other water bodies in the future.