bluuebunny/crossref_metadata_2025 huggingface dataset:
An Acid‐Controlled Method for the Regioselective Functionalization of Anilines over Aliphatic Amines
Authors: Li Bowen , Hu Yulun , Tochtrop Gregory P.
Published: August 2023

Regioselective transformations at similar functional groups are of paramount importance in organic synthesis. Traditional strategies towards regioselective functionalization include serial protection/deprotection and sequential synthesis. Modern organic synthesis emphasizes pathway efficiency and protecting group free routes with a goal of exploiting inherent differences in reactivity. This study reports a method for the regioselective functionalization of anilines over aliphatic amines. Utilizing classic conditions for the Baeyer‐Mills reaction, anilines were shown to react preferentially in the presence of aliphatic amines. Subsequently, this principle of reactivity was extended to other electrophiles and conditions.
Transition Metal Ions Influence the Performance of Photodetector of Two‐Dimensional CdS Nanoplatelets
Authors: Medda Anusri , Ghosh Soubhik , Patra Amitava
Published: August 2023

Transition metal‐doped two‐dimensional (2D) semiconductor nanoplatelets (NPLs) with atomically precise thickness have attracted much research interest due to their inherent photo‐physical properties. In this work, we have synthesized 2D Cu‐doped CdS NPLs, investigated the charge transfer dynamics using ultrafast transient absorption spectroscopy, and fabricated an efficient photodetector device. A large Stoke's shifted emission at ~685 nm with an average lifetime of about ~1.45 μs is observed in Cu‐doped CdS NPLs. Slower bleach recovery kinetics leads to large charge carrier separation in Cu‐doped NPLs which is beneficial for photodetector applications. Cu‐doped NPLs‐based photodetectors exhibit high photocurrent, fast response (~120 ms), ~600 times higher photoresponsivity, and ~300 times higher detectivity (~4.1×1013 Jones) than undoped CdS NPLs. These excellent properties of Cu‐doped CdS NPLs make this material an efficient alternative for next‐generation optoelectronic devices.
2,4,5,7‐Tetranitrofluorenone Oximate for the Naked‐Eye Detection of H‐Bond Donors and the Chiroptical Sensing of Enantiopure Reagents
Authors: Pál Dávid , Besnard Céline , de Aguirre Adiran , Poblador‐Bahamonde Amalia I. , Pescitelli Gennaro , Lacour Jérôme
Published: August 2023

Hydrogen bonding greatly influences rates and equilibrium positions of chemical reactions, conformations, and sometimes even stereochemistry. This study reports on tetranitrofluorenone oximate, a novel dye capable of naked‐eye detection of hydrogen‐bond donating species (HBDs) and of rapid determination of H‐bond donation strength by hypsochromic shift monitoring. In addition, the molecule possesses atropisomeric conformations, of M and P configuration, as evidenced in solid and solution state studies by X‐ray diffraction and electronic circular dichroism (ECD), respectively. In the latter case, enantiopure bis‐thioureas were the most effective HBDs to promote a chiral induction (diastereoselective recognition, Pfeiffer effect); the ECD results being rationalized by time‐dependent density functional theory (TDDFT) calculations. Based on these experiments, bis‐thioureas were used as chiral reagents in asymmetric 1,3‐dipolar cycloadditions of structurally‐related nitrones; the ECD sensing of the stereoinduction between bis‐thioureas and the oximate serving as an indirect method of selection of the most effective HBD for asymmetric synthesis.
Schlenk‐Type Equilibria of Grignard‐Analogous Arylberyllium Complexes: Steric Effects**
Authors: Helling Christoph , Jones Cameron
Published: August 2023

The presence of complex Schlenk equilibria is a central property of synthetically invaluable Grignard reagents substantially affecting their reactivity and selectivity in chemical transformations. In this work, the steric effects of aryl substituents on the Schlenk‐type equilibria of their lighter congeners, arylberyllium bromides, are systematically studied. Combination of diarylberyllium complexes Ar2Be(OEt2) (1Ar, Ar=Tip, Tcpp; Tip=2,4,6‐iPr3C6H3, Tcpp=2,4,6‐Cyp3C6H3, Cyp=c‐C5H9), containing sterically demanding aryl groups, and BeBr2(OEt2)2 (2) affords the Grignard‐analogous arylberyllium bromides ArBeBr(OEt2) (3Ar, Ar=Tip, Tcpp). In contrast, Mes2Be(OEt2) (1Mes, Mes=2,4,6‐Me3C6H3) and 2 exist in a temperature‐dependent equilibrium with MesBeBr(OEt2) (3Mes) and free OEt2. Ph2Be(OEt2) (1Ph) reacts with 2 to afford dimeric [PhBeBr(OEt2)]2 ([3Ph]2). Moreover, the influence of replacing the OEt2 donor by an N‐heterocyclic carbene, IPr2Me2 (IPr2Me2=C(iPrNCMe)2), on the redistribution reactions was investigated. The solution‐ and solid‐state structures of the diarylberyllium and arylberyllium bromide complexes were comprehensively characterized using multinuclear (1H, 9Be, 13C) NMR spectroscopic methods and single‐crystal X‐ray diffraction, while DFT calculations were employed to support the experimental findings.
Diversification and deleterious role of microbiome in gastric cancer
Authors: Chattopadhyay Indranil , Gundamaraju Rohit , Rajeev Ashwin
Published: August 2023

Gut microbiota dictates the fate of several diseases, including cancer. Most gastric cancers (GC) belong to gastric adenocarcinomas (GAC). Helicobacter pylori colonizes the gastric epithelium and is the causative agent of 75% of all stomach malignancies globally. This bacterium has several virulence factors, including cytotoxin‐associated gene A (CagA), vacuolating cytotoxin (VacA), and outer membrane proteins (OMPs), all of which have been linked to the development of gastric cancer. In addition, bacteria such as Escherichia coli, Streptococcus, Clostridium, Haemophilus, Veillonella, Staphylococcus, and Lactobacillus play an important role in the development of gastric cancer. Besides, lactic acid bacteria (LAB) such as Bifidobacterium, Lactobacillus, Lactococcus, and Streptococcus were found in greater abundance in GAC patients. To identify potential diagnostic and therapeutic interventions for GC, it is essential to understand the mechanistic role of H. pylori and other bacteria that contribute to gastric carcinogenesis. Furthermore, understanding bacteria‐host interactions and bacteria‐induced inflammatory pathways in the host is critical for developing treatment targets for gastric cancer.
Liposome Based Near‐Infrared Sensors for the Selective Detection of Hydrogen Sulfide
Authors: Kumar Vinod , Sakla Rahul , Sharma Nancy , Kanika  , Khan Rehan , Jose D. Amilan
Published: August 2023

Cyanine dye‐based new amphiphilic compound NIR‐Amp has been synthesised. NIR‐Amp was embedded with phospholipids DOPC and DPPC to form liposomes based nanoscale chemical sensors NIR‐Lip1 and NIR‐Lip2. Here, two different phospholipids were used to demonstrate the influence of lipid structure, composition and fluidity on sensing of nanosensors. Both the probes show NIR absorption maximum at 790 nm and emission maximum at 815 nm. H2S‐triggered thiolation resulted a remarkable change in color from green to pale yellow. A decrease in UV‐Vis absorption and emission in the NIR region was observed only with H2S. NIR‐Lip1 and NIR‐Lip2 are highly selective for H2S with a LOD of 0.57 μM and 1.24 μM, respectively. It was observed that in a solid‐like gel state, NIR‐Lip1 is slightly more sensitive towards H2S than fluid‐like NIR‐Lip2. The H2S sensing mechanism was confirmed by ESI‐mass and infrared (IR) spectroscopic analysis. Based on the high sensitivity and selectivity, NIR‐Lip1 was employed to detect H2S in vegetable samples. Further, the probes are found to be non‐toxic and established for H2S fluorescence imaging in live cells.
The Importance of Precise Reaction Condition Control for the Comparison of Photocatalyst Materials on the Example of Hydrogen Peroxide Formation over Polymeric Carbon Nitrides
Authors: Wegstein Deborah , Zaim Abdelkarim , Burek Bastien O. , Bloh Jonathan Z.
Published: August 2023

In our study, we aimed to show how different reaction parameters can affect production rates using photocatalytic hydrogen peroxide formation by different polymeric carbon nitrides (PCN). For this purpose, selected materials were first compared under the same reaction conditions and compared with TiO2 (P25). We also show that different light intensities can have a different influence on seemingly similar materials. Since hydrogen peroxide production in the presence of an electron donor proceeds mainly by reduction of oxygen, we also show an influence of the oxygen flow on the formation rates. Thus, with high oxygen fluxes and high intensities of irradiated light, we were able to achieve an H2O2 concentration of 125 mM after about 25 h. Finally, the two best PCN materials were selected to measure light intensity dependence at different wavelengths up to visible light. It was found that they behaved differently at the different wavelengths and thus it could be shown that an exact specification of the reaction parameters is indispensable for comparisons in the literature.
A null allele of the polyphenol oxidase gene Ppo‐A1 in hexaploid wheat originates from tetraploid wheat
Authors: Nakamaru Akiko , Kato Keita , Ikenaga Sachiko , Nakamura Toshiki
Published: August 2023

Polyphenol oxidase (PPO) has a major effect on the time‐dependent darkening of noodle products. Development of varieties with low PPO activity is one method to eliminate this problem and respond to the demands of consumers. Among the common wheat (Triticum aestivum L.) Ppo genes, Ppo‐A1 has the highest effect on grain PPO activity, and several Ppo‐A1 alleles with low or no activity have been reported, with the recently identified Ppo‐A1i allele being the most desirable allele. In this study, reverse‐transcription polymerase chain reaction analysis confirmed that this allele was not expressed and was therefore functionally null. We also determined that Ppo‐A1i has an approximately 3 kb insertion in the second intron. Taking advantage of the insertion sequence, we developed a new co‐dominant marker, PPO18Plus, capable of distinguishing Ppo‐A1a, Ppo‐A1b, and Ppo‐A1i. In addition, we determined that the Ppo‐A1i allele is identical to and originates from the Ppo‐A1g allele of tetraploid wheat. The durum wheat (Triticum turgidum ssp. durum (Desf.) Husn.) Ppo‐A1g allele has been used to improve pasta color in durum wheat breeding programs. Thus, the PPO18Plus marker developed here will be very useful in both hexaploid and durum wheat breeding programs.
The security‐based optimization algorithm for enhancing the energy efficiency of wireless sensor networks
Authors: Anusha Sowbarnika V. , Balasubramani M. , Kavitha K.
Published: August 2023

In the upcoming era, one of the emergent technologies is “Wireless Sensor Networks (WSNs),” which has provided various solutions in the field of defense, surveillance, and so on. But the main problems in the WSNs are security and energy‐efficient routing to the researchers. The deployment of security algorithms can monitor only the unauthorized signals to ensure security, but it lacks and leads to higher energy consumption, whereas the deployment of energy‐efficient routing algorithms is used only for the selection of routing paths, but it fails to ensure security. Hence, the main intent of this research work is to solve both problems by the following proposed models. Model 1 is “Identity‐Based Aggregate Signatures (IBAS)” that is the most effective security‐based framework protocol in this research work. Model 2 is the integration of IBAS and “Fuzzy Logic System (FLS)” that acts as an energy‐efficient algorithm, and here, FLS is used to find the optimal path from source to destination to transmit the data. Model 3 is the combination of IBAS and the “Whale Optimization Algorithm (WOA)” for higher energy efficiency and auto localization by analyzing the entire route in WSN. Model 4 is the combination of IBAS, WOA, and the “Reinforcement Theory of WOA (RTWOA)” energy‐efficiency model with a twofold and weight factor strategy for better speed and accuracy. These models ensure security, energy efficiency, and auto localization. The simulation parameters such as “Energy Efficiency,” “Packet Delivery Ratio,” “Average delay,” “Throughput,” and “Energy Consumption” are evaluated, and results show that the performance of energy efficiency and security is higher in Model 4 when compared to the other three models.
Supraclavicular lymph nodes: An easily accessible site for diagnosis and molecular profiling of malignancies in the era of precision medicine
Authors: Bailey Gabrielle E. , Maleki Zahra
Published: August 2023

Background

The supraclavicular lymph node (SCN) is a common metastatic site for malignancies of supra and infra‐diaphragmatic origin and is easily accessible for small biopsy and fine needle aspiration (FNA). In this study, the utility of SCN biopsies was analyzed for diagnosis and ancillary studies.

Methods

The electronic pathology archive was searched for cases of FNA of SCNs accompanied by small core biopsies (1/2016–12/2018). The patients' demographics, diagnosis, and ancillary studies were recorded.

Results

Eighty‐eight cases were reviewed (49 females and 39 males), with patients' ages ranging from 23 to 84 years (mean = 52.85 years). Fifty‐four (61.4%) specimens were from the left SCN and thirty‐four (38.6%) from the right. All FNA cases were performed by a radiologist under ultrasound guidance and rapid on‐site evaltion (ROSE) was performed by a cytologist. Nineteen cases (21.6%) were benign and sixty‐nine cases were malignant (78.4%). Carcinoma was the most common malignant neoplasm (52.3%) including 38.2% (13/34) of the right SCN and 61.1% (33/54) of the left SCN cases. Metastatic lung and breast adenocarcinomas (9.1% each) were the most common carcinomas overall. Lymphoma was the second most common malignancy (17.0%) including 17.6% (6/34) of the right SCN and 16.7% (9/54) of the left SCN cases. The majority of cases were accomponied by ancillary studies for diagnosis and prognostic markers. Ancillary studies included immunostains (63 cases, 71.6%), PD‐L1 testing (21 cases, 23.9%), FISH testing (7 cases, 8.0%), flow cytometry (20 cases, 22.7%) and NGS studies (8 cases, 9.1%).

Conclusion

Supraclavicular lymph nodes are easily accessible and diagnostically useful sites for detection of malignancies and molecular alterations responsive to targeted or immune therapy.
What are the cognitive‐linguistic profiles and subtypes of Chinese adolescents with dyslexia?
Authors: Chan Kevin , Chung Kevin Kien Hoa , Lam Chun Bun
Published: August 2023

While research has identified multiple deficits that may lead to dyslexia, the profiles of adolescents with dyslexia and dyslexia subtypes are yet fully understood. This study examined the profiles of Chinese adolescents with dyslexia and identified dyslexia subtypes. Adolescents from grades 7 to 9 (n = 184, 92 with dyslexia) were evaluated on morphological skills, visual‐orthographic knowledge, rapid naming, working memory, word reading, word spelling, reading fluency and reading comprehension. The results revealed that adolescents with dyslexia performed less well on the cognitive‐linguistic and literacy measures than typically developing adolescents. A logistic regression analysis also showed that morphological skills, visual‐orthographic knowledge and rapid naming were significantly predictive of dyslexia status. Using cluster analysis and guided by the multiple deficit hypothesis, this study identified four dyslexia subtypes: morphological deficit, visual‐orthographic knowledge deficit, rapid naming deficit and global deficit showing multiple cognitive‐linguistic and literacy problems. Understanding the profiles and subtypes of dyslexia could enable educational psychologists and educators to select appropriate assessment measures and develop intervention strategies to support the learning of Chinese adolescents with dyslexia.
Improvements in cardiovascular disease risk factors associated with modest weight loss following treatment in patients with binge‐eating disorder and obesity
Authors: Yurkow Sydney , Ivezaj Valentina , Grilo Carlos M.
Published: August 2023

Background

Modest weight losses may be associated with improvements in cardiovascular disease risk factors (CVDRF) in patients with obesity. The effects of weight losses on CVDRF in persons with binge‐eating disorder (BED) are unknown. This study prospectively examined changes in CVDRF among patients receiving behaviorally‐based weight‐loss treatment (BBWLT) who attained modest weight losses (≥5 to <10% and ≥10%).

Method

Of 191 participants, CVDRF variables were re‐assessed in 168 participants at posttreatment and in 151 at 12‐month follow‐up. Participants who attained ≥5 to <10% weight loss were compared to those who did not on CVDRFs (total cholesterol, HDL, LDL, triglycerides, HbA1C, mean plasma glucose, heart rate, and systolic/diastolic blood pressure); similar comparisons were completed for those who attained ≥10% weight loss.

Results

At posttreatment, ≥5 to <10% weight loss (N = 42; 25.0%) was associated with significant improvements in HbA1c and mean plasma glucose, whereas ≥10% weight loss (N = 40, 23.8%) was associated with significant improvements in total cholesterol, triglycerides, HbA1c, mean plasma glucose, and heart rate. At 12‐month follow‐up, ≥5 to <10% weight loss (N = 17; 11.1%) was related to significant improvements on HDL, triglycerides, HbA1c, and mean plasma glucose, whereas ≥10% weight loss (N = 40, 26.0%) was associated with significant improvements on all the CVDRF variables (except blood pressure).

Conclusions

Modest weight loss is associated with significant improvements in CVDRFs in patients with BED and obesity following treatment and at 12‐month follow‐up. Future work should examine whether improvements in CVDRF are attributable to weight loss per se and/or to other related lifestyle changes.

Public significance statement

Individuals with binge‐eating disorder and obesity who attain modest weight loss following treatment exhibit improvements in various measures of cardiovascular disease risk compared to those who do not. While weight loss has been challenging for individuals with binge‐eating disorder, clinicians should inform patients of the potential health benefits of modest weight loss. Future research should investigate whether weight loss itself and/or related behavioral lifestyle changes drive improved cardiovascular disease risk factors.
Trimetazidine in heart failure with preserved ejection fraction: a randomized controlled cross‐over trial
Authors: van de Bovenkamp Arno A. , Geurkink Kiki T. J. , Oosterveer Frank T.P. , de Man Frances S. , Kok Wouter E.M. , Bronzwaer Patrick N.A. , Allaart Cor P. , Nederveen Aart J. , van Rossum Albert C. , Bakermans Adrianus J. , Handoko M. Louis
Published: August 2023

Aims

Impaired myocardial energy homeostasis plays an import role in the pathophysiology of heart failure with preserved ejection fraction (HFpEF). Left ventricular relaxation has a high energy demand, and left ventricular diastolic dysfunction has been related to impaired energy homeostasis. This study investigated whether trimetazidine, a fatty acid oxidation inhibitor, could improve myocardial energy homeostasis and consequently improve exercise haemodynamics in patients with HFpEF.

Methods and results

The DoPING‐HFpEF trial was a phase II single‐centre, double‐blind, placebo‐controlled, randomized cross‐over trial. Patients were randomized to trimetazidine treatment or placebo for 3 months and switched after a 2‐week wash‐out period. The primary endpoint was change in pulmonary capillary wedge pressure, measured with right heart catheterization at multiple stages of bicycling exercise. Secondary endpoint was change in myocardial phosphocreatine/adenosine triphosphate, an index of the myocardial energy status, measured with phosphorus‐31 magnetic resonance spectroscopy. The study included 25 patients (10/15 males/females; mean (standard deviation) age, 66 (10) years; body mass index, 29.8 (4.5) kg/m2); with the diagnosis of HFpEF confirmed with (exercise) right heart catheterization either before or during the trial. There was no effect of trimetazidine on the primary outcome pulmonary capillary wedge pressure at multiple levels of exercise (mean change 0 [95% confidence interval, 95% CI −2, 2] mmHg over multiple levels of exercise, P = 0.60). Myocardial phosphocreatine/adenosine triphosphate in the trimetazidine arm was similar to placebo (1.08 [0.76, 1.76] vs. 1.30 [0.95, 1.86], P = 0.08). There was no change by trimetazidine compared with placebo in the exploratory parameters: 6‐min walking distance (mean change of −6 [95% CI −18, 7] m vs. −5 [95% CI −22, 22] m, respectively, P = 0.93), N‐terminal pro‐B‐type natriuretic peptide (5 (−156, 166) ng/L vs. −13 (−172, 147) ng/L, P = 0.70), overall quality‐of‐life (KCCQ and EQ‐5D‐5L, P = 0.78 and P = 0.51, respectively), parameters for diastolic function measured with echocardiography and cardiac magnetic resonance, or metabolic parameters.

Conclusions

Trimetazidine did not improve myocardial energy homeostasis and did not improve exercise haemodynamics in patients with HFpEF.
Regional expert opinion: Management of heart failure with preserved ejection fraction in the Middle East, North Africa and Turkey
Authors: Abdelhamid Magdy , Al Ghalayini Kamal , Al‐Humood Khaldoon , Altun Bülent , Arafah Mohammed , Bader Feras , Ibrahim Mohamed , Sabbour Hani , Shawky Elserafy Ahmed , Skouri Hadi , Yilmaz Mehmet Birhan
Published: August 2023

Although epidemiological data on heart failure (HF) with preserved ejection fraction (HFpEF) are scarce in the Middle East, North Africa and Turkey (MENAT) region, Lancet Global Burden of Disease estimated the prevalence of HF in the MENAT region in 2019 to be 0.78%, versus 0.71% globally. There is also a high incidence of HFpEF risk factors and co‐morbidities in the region, including coronary artery disease, diabetes, obesity, hypertension, anaemia and chronic kidney disease. For instance, 14.5–16.2% of adults in the region reportedly have diabetes, versus 7.0% in Europe. Together with increasing life expectancy, this may contribute towards a higher burden of HFpEF in the region than currently reported. This paper aims to describe the epidemiology and burden of HFpEF in the MENAT region, including unique risk factors and co‐morbidities. It highlights challenges with diagnosing HFpEF, such as the prioritization of HF with reduced ejection fraction (HFrEF), the specific profile of HFpEF patients in the region and barriers to effective management associated with the healthcare system. Guidance is given on the diagnosis, prevention and management of HFpEF, including the emerging role of sodium‐glucose co‐transporter‐2 inhibitors. Given the high burden of HFpEF coupled with the fact that its prevalence is likely to be underestimated, healthcare professionals need to be alert to its signs and symptoms and to manage patients accordingly. Historically, HFpEF treatments have focused on managing co‐morbidities and symptoms, but new agents are now available with proven effects on outcomes in patients with HFpEF.
Experimental and Theoretical Study of the Features of Zinc(II) and Cadmium(II) Complexation with the Substitutedcloso‐Hydridoborate Anion [2‐B10H9(OH)]2−
Authors: Nikiforova Svetlana E. , Matveev Evgeniy Y. , Kubasov Alexey S. , Golubev Alexey V. , Goeva Lyudmila V. , Malinina Elena A. , Zhizhin Konstantin Y. , Kuznetsov Nikolay T.
Published: August 2023

Herein, we studied the experimental and theoretical foundations of the process of zinc(II) and cadmium(II) complexation with 2‐hydroxido‐nonahydrido‐closo‐decaborate(2−) anion [2‐B10H9(OH)]2−in the presence of azaheterocyclic ligands L (L=2,2′‐bipyridyl (bipy), 1,10‐phenanthroline (phen), and 2,2′‐bipyridylamine (bpa)), which can be used as model system for obtaining complexes with the required composition and structure. The first examples of mixed‐ligand Zn(II) and Cd(II) complexes with [2‐B10H9(OH)]2−coordinated by the metal atom were isolated selectively. The structures of zinc(II) complexes [Zn(bipy)2(2‐B10H9(OH)‐κ2H1,O)] ⋅ 2CH3CN (1 ⋅ 2CH3CN) and [Zn(phen)2(2‐B10H9(OH)‐κ2H9,O)] ⋅ 2CH3CN (2 ⋅ 2CH3CN), as well as two cadmium(II) bond isomers [Cd(bipy)2(2‐B10H9(OH)‐κ2H1,O)] (4 a) and [Cd(bipy)2(2‐B10H9(OH)‐κ2H9,H10)] (4 b) bound into a dimeric pair in the complex [Cd(bipy)2(2‐B10H9(OH))] (4), and cadmium(II) complex [Cd(bpa)2(2‐B10H9(OH)‐κ2H7,H10)] (7) were solved by single‐crystal X‐ray diffraction (XRD). Density functional theory (DFT) calculations show that for cadmium(II) the formation of both multicenter BH−Cd−HB and BO(H)−Cd−HB bonds is equally probable. The affinity of zinc(II) for oxygen leads to preferential formation of complexes via BO(H)−Zn−HB bonds than BH−Zn−HB bonds. The M−B(H) bonding was found to be presumably electrostatic in nature, which could be the reason of topological isomerism of zinc(II) and cadmium(II) decaborates.
How Ligand Geometry Affects the Reactivity of Co(II) Cyclam Complexes
Authors: Iffland‐Mühlhaus Linda , Battistella Beatrice , Siegmund Daniel , Ray Kallol , Apfel Ulf‐Peter
Published: August 2023

Cobalt complexes are extensively studied as bioinspired models for non‐heme oxygenases as they facilitate both the stabilization and characterization of metal‐oxygen intermediates. As an analog to the well‐known Co(cyclam) complex Co{N4} (cyclam=1,4,8,11‐tetraazacyclotetradecane), the CoII complex Co{i‐N4} with the isomeric isocyclam ligand (isocyclam=1,4,7,11‐tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N4 donor set of both complexes, Co{i‐N4} enables the 2e−/2H+ reduction of O2 with a lower overpotential (ηeff of 385 mV vs. 540 mV for Co{N4}), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O2 activation of Co{i‐N4} reveals a structurally identified stable μ‐peroxo CoIII dimer as the main product. A superoxo CoIII species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O2 species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6‐tetramethylpiperidin‐1‐ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i‐N4} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes.
Microfluidic isolation of breast cancer circulating tumor cells from microvolumes of mouse blood
Authors: Macaraniag Celine , Zhou Jian , Li Jing , Putzbach William , Hay Nissim , Papautsky Ian
Published: August 2023

Liquid biopsy has shown significant research and clinical implications in cancer. Particularly, the isolation of circulating tumor cells (CTCs) in preclinical studies can provide crucial information about disease progression and therefore may guide treatment decisions. Microfluidic isolation systems have played a considerable role in CTC isolation for cancer studies, disease diagnosis, and prognosis. CTCs are often studied using preclinical animal models such as xenografts or syngeneic models. However, most isolation systems are tested on human cell lines and human blood, whereas less validation studies are done on preclinical samples such as CTCs from mouse models. Here, we demonstrate and evaluate a complete workflow of a sized‐based inertial microfluidic device to isolate CTCs from blood using exclusively mouse blood and mouse cancer cell lines. We then incorporate the cytospin, a commonly used method for enumeration of small number of cells in a glass slide to quantify the total cell yield of our workflow.
Learning‐based containment control in the absence of leaders' information
Authors: Zhao Yong , Fan Hanning , Guan Sihai
Published: August 2023

This article considers the containment control problem of continuous‐time dynamic agents without leaders' state information. The leaders have first‐ and second‐order dynamics, respectively, while first‐order dynamics always govern the followers. Each agent has inherent nonlinear dynamics and can only measure the output information of its neighbors. The output of each leader is expressed as the product of an unknown coefficient and a position‐like state, while the output of each follower is equal to its position‐like state. To stabilize the position‐like states of the followers to the convex hull spanned by leaders, the unknown coefficients are asymptotically tracked by leveraging reinforcement learning based on the inherent dynamics and the output information. Two distributed learning‐based containment protocols are proposed, respectively. It is proved that if the directed communication topology has a spanning forest and certain conditions in terms of the inherent nonlinear dynamics are satisfied, then the proposed controllers with proper control gains solve the containment control problem asymptotically under arbitrary initial states. An exciting conclusion is that the learning algorithms' convergence rate plays an important role in achieving containment control. Numerical simulations are performed to validate the effectiveness of the obtained theoretical results.
Geoarchaeological and microstratigraphic view of a Neanderthal settlement at Rambla de Ahíllas in Iberian Range: Abrigo de la Quebrada (Chelva, Valencia, Spain)
Authors: Bergadà M. Mercè , Eixea Aleix , Villaverde Valentín
Published: August 2023

The Abrigo de la Quebrada is a Middle Palaeolithic rockshelter located in the Rambla de Ahíllas in the Iberian Range (Valencia, Spain). Archaeological work began in 2007 and was completed in 2015, reaching the rockshelter substratum and uncovering a record that spans from MIS 5 to MIS 4/3. The data from the geoarchaeological and micromorphological study of the site allow us to deduce that it was formed by alluvial contributions from the ephemeral stream, in different subenvironments varying from channel/bar to floodplain facies. These alternate with debris from different displacement processes depending on the unit, such as solifluction–gelifluction, mass displacement, and diffuse runoff. In addition, collapse episodes of the overhanging rockshelter roof influenced the pedological evolution of the record, with implications for the archaeological levels, especially in Unit G (Level IV). From a paleoenvironmental point of view, a more contrasted variability is reflected in the upper units of the site (MIS 4/3), especially in Unit G (Level IV), which, based on data, suggests temperate conditions, and in Unit H (Levels III and II) indicate cold conditions. In contrast, the lower units (MIS 5) are generally temperate, with the exception of Unit C (Level VIIIa), which reflects a colder phase.
Reliability and validity of brain‐gastric phase synchronization
Authors: Levakov Gidon , Ganor Shira , Avidan Galia
Published: August 2023

Recent studies have reported that various brain regions, mainly sensory, unimodal regions, display phase synchronization with the stomach's slow (0.05 Hz) myoelectrical rhythm. These gastric–brain interactions have broad implications, from feeding behavior to functional gastrointestinal disorders. However, in contrast to other interoceptive signals (e.g., heart rate) and their relation to the brain, little is known about the reliability of these gastric–brain interactions, their robustness to artifacts such as motion, and whether they can be generalized to new samples. Here we examined these aspects in 43 subjects that had undergone multiple runs of concurrent electrogastrography (EGG), brain fMRI, and pulse oximetry. We also repeated all analyses in an open dataset of a highly sampled individual. We found a set of brain regions that were coupled with the EGG signal after controlling for non‐grey matter (GM) signals, head motion, and cardiac artifacts. These regions exhibited significant overlap with previous work. However, we also showed that prior to confound regression, the spatial extent of the gastric network was largely overestimated. Finally, we found substantial test–retest reliability in both the brain and the gastric signals when estimated alone, but not for measures of gastric‐brain synchrony. Together, these results provide methodological scaffolding for future research into brain–stomach interactions and for a better understanding of the role of the gastric network.
The role of neurotransmitters in mediating the relationship between brain alterations and depressive symptoms in patients with inflammatory bowel disease
Authors: Wang Jun , Liu Guangyao , Xu Kun , Ai Kai , Huang Wenjing , Zhang Jing
Published: August 2023

A growing body of evidence from neuroimaging studies suggests that inflammatory bowel disease (IBD) is associated with functional and structural alterations in the central nervous system and that it has a potential link to emotional symptoms, such as anxiety and depression. However, the neurochemical underpinnings of depression symptoms in IBD remain unclear. We hypothesized that changes in cortical gamma‐aminobutyric acid (GABA+) and glutamine (Glx) concentrations are related to cortical thickness and resting‐state functional connectivity in IBD as compared to healthy controls. To test this, we measured whole‐brain cortical thickness and functional connectivity within the medial prefrontal cortex (mPFC), as well as the concentrations of neurotransmitters in the same brain region. We used the edited magnetic resonance spectroscopy (MRS) with the MEGA‐PRESS sequence at a 3 T scanner to quantitate the neurotransmitter levels in the mPFC. Subjects with IBD (N = 37) and healthy control subjects (N = 32) were enrolled in the study. Compared with healthy controls, there were significantly decreased GABA+ and Glx concentrations in the mPFC of patients with IBD. The cortical thickness of patients with IBD was thin in two clusters that included the right medial orbitofrontal cortex and the right posterior cingulate cortex. A seed‐based functional connectivity analysis indicated that there was higher connectivity of the mPFC with the left precuneus cortex (PC) and the posterior cingulate cortex, and conversely, lower connectivity in the left frontal pole was observed. The functional connectivity between the mPFC and the left PC was negatively correlated with the IBD questionnaire score (r = −0.388, p = 0.018). GABA+ concentrations had a negative correlation with the Hamilton Depression Scale (HAMD) score (r = −0.497, p = 0.002). Glx concentration was negatively correlated with the HAMD score (r = −0.496, p = 0.002) and positively correlated with the Short‐Form McGill Pain Questionnaire score (r = 0.330, p = 0.046, uncorrected). There was a significant positive correlation between the ratio of Glx to GABA+ and the HAMD score (r = 0.428, p = 0.008). Mediation analysis revealed that GABA+ significantly mediated the main effect of the relationship between the structural and functional alterations and the severity of depression in patients with IBD. Our study provides initial evidence of neurochemistry that can be used to identify potential mechanisms underlying the modulatory effects of GABA+ on the development of depression in patients with IBD.
Design matters: A comparison of natural versus synthetic skin substitutes across benchtop and porcine wound healing metrics: An experimental study
Authors: Stefanelli Victoria L. , Mintz Benjamin , Gandhi Ankur , Smith Jason
Published: August 2023

Background and Aims

Skin substitutes, essential tools for helping close full thickness wounds with minimal scarring, are available in both collagen‐based and synthetic polyurethane constructions. Here we explore fundamental differences between two frequently used skin substitutes and discuss how these differences may impact in vivo performance.

Methods

Polyurethane‐ and collagen‐based matrices were characterized in vitro for pore size via scanning electron microscopy, hydrophobicity via liquid contact angle, conformability via bending angle, and biocompatibility via fibroblast and keratinocyte adhesion and proliferation. These matrices were then evaluated in a full‐thickness excisional pig wound study followed by histological analysis. Statistical analysis was performed using t‐tests or one‐way analysis of variances with Tukey's multiple post hoc comparisons, where appropriate.

Results

Average pore diameter in the tested polyurethane matrix was over four times larger than that of the collagen matrix (589 ± 297 µm vs. 132 ± 91 µm). Through liquid contact angle measurement, the collagen matrix (not measurable) was found to be hydrophilic compared to the hydrophobic polyurethane matrix (>90°). The collagen matrix was significantly more conformable than the polyurethane matrix (9 ± 2° vs. 84 ± 5° bending angle, respectively). Fibroblast and keratinocyte adhesion and proliferation assays elucidated a significantly greater ability of both cell types to attach and proliferate on collagen versus polyurethane. While the porcine study showed minimal contraction of either matrix material, histological findings between the two treatments were markedly different. Collagen matrices were associated with early fibroblast infiltration and fibroplasia, whereas polyurethane matrices elicited a strong multinucleated giant cell response and produced a network of comparatively aligned collagen fibrils.

Conclusions

The more favorable in vitro properties of the collagen matrix led to less inflammation and better overall tissue response in vivo. Overall, our findings demonstrate how the choice of biomaterial and its design directly translate to differing in vivo mechanisms of action and overall tissue quality.
Cross‐border insolvency law of China: An empirical analysis and proposal based on the insolvency cooperation mechanism between the Chinese mainland and Hong Kong
Authors: Zhang Haizheng , Huang Yapei
Published: August 2023

In the context of the national strategy of the construction of the Guangdong‐Hong Kong‐Macao Greater Bay Area, the first institutional breakthrough in cross‐border insolvency cooperation between the Chinese Mainland and Hong Kong was achieved on 14 May 2021, and the first case of recognition and assistance in insolvency proceedings in Hong Kong, Re Samson Paper Co Ltd., emerged in judicial practice in December 2021. The judicial practice of Samson not only successfully verifies the great significance of the Record of Meeting and the Opinion for institutional ice‐breaking of cross‐border insolvency cooperation in the Chinese Mainland, but also reflects the practical effects and legislative issues of the above documents on the mechanism of insolvency cooperation between two areas. In view of the problems reflected by the practice of Re Samson Paper Co Ltd. and existing in the legislation, this paper puts forward specific proposals for the cross‐border insolvency cooperation between the Chinese Mainland and Hong Kong, including abolishing the precondition of reciprocity, strengthening exchanges, and cooperation between the two areas on parallel bankruptcy issues, and supplementing the coordination of parallel bankruptcy procedures for cross‐border insolvency. It also proposes domestic legislation on cross‐border insolvency recognition and assistance in China in a point‐by‐point manner, so as to achieve the establishment of a sound cross‐border insolvency cooperation mechanism in line with the international community.
Relationship focused mother–infant groups: Preliminary evaluation of improvements in maternal mental health, parenting confidence, and parental reflective functioning
Authors: Cooke Sharon , Cooke Dawson Campbell , Hauck Yvonne
Published: August 2023

We report on two preliminary evaluations of a group intervention, targeting vulnerable infants and their mothers within the first 6‐months postpartum. The Mother–Baby Nurture® program aims to strengthen the developing infant–mother attachment relationship by increasing maternal mentalizing. These studies were undertaken with pre‐post evaluations with the mothers of infants under 10‐months of age. The mother–infant dyads participated in ten 2‐h group sessions. Study one (N = 69 dyads) included self‐reported maternal depression, anxiety, and parenting confidence. In study two (N = 27 dyads), parenting stress and reflective functioning were measured by self‐report, and reflective functioning coded on the 5 min speech sample (completed by N = 22). Results from study one confirmed a decrease in depression (p < .001, d = .79) and anxiety (p < .001, d = .72) symptoms, and an increase in mothers’ scores for parenting confidence (p < .001, d = −.98). Results from Study Two demonstrated a significant decrease in parenting stress (p < .001, d = .94) and significant improvement in measures of self‐report reflective functioning (p = .007, .024; d = .56, .61). These findings are preliminary yet promising indications that this program could be effective in alleviating parenting stress, depression, and anxiety, and improving mother's reflective functioning and parenting confidence. Further research is needed, with a control group and long‐term follow‐up assessments.
Environmentally realistic concentrations of chlorinated, brominated, and fluorinated persistent organic pollutants induce the unfolded protein response as a shared stress pathway in the liver of Atlantic cod (Gadus morhua)
Authors: Olsvik Pål A. , Meier Sonnich , Zhang Xiaokang , Goksøyr Anders , Karlsen Odd Andre , Yadetie Fekadu
Published: August 2023

In the North Sea and North Atlantic coastal areas, fish experience relatively high background levels of persistent organic pollutants. This study aimed to compare the mode of action of environmentally relevant concentrations of mixtures of halogenated compounds in Atlantic cod. Juvenile male cod with mean weight of 840 g were exposed by gavage to dietary mixtures of chlorinated (PCBs, DDT analogs, chlordane, lindane, and toxaphene), brominated (PBDEs), and fluorinated (PFOS) compounds for 4 weeks. One group received a combined mixture of all three compound groups. The results showed that the accumulated levels of chemicals in cod liver after 4 weeks of exposure reflected concentrations found in wild fish in this region. Pathway analysis revealed that the treatment effects by each of the three groups of chemicals (chlorinated, brominated, and fluorinated) converged on activation of the unfolded protein response (UPR). Upstream regulator analysis predicted that almost all the key transcription factors (XBP1, ERN1, ATF4, EIF2AK3, and NFE2L2) regulating the UPR were significantly activated. No additive effect was observed in cod co‐treated with all three compound groups. In conclusion, the genome‐wide transcriptomic study suggests that the UPR pathway is a sensitive common target of halogenated organic environmental pollutants in fish.
Extracorporeal membrane oxygenation and effects on tendon tissue: A vibrational spectroscopy study
Authors: Stefani Sara , Govoni Marco , Tombolesi Niki , Vivarelli Leonardo , Dallari Dante , Paolantoni Marco , Sassi Paola , Morresi Assunta
Published: August 2023

Extracorporeal membrane oxygenation (ECMO) is an invasive medical technique used to provide life support in persons with insufficient cardiac and respiratory functionalities, or to preserve, postmortem, and organ function addressing organ/tissue transplant. Although a lot of information is available about organs in their entirety, the safety and effectiveness of allogeneic tissues collected from ECMO donors have not been fully elucidated. In this preliminary study, samples of tibial and peroneal human tendons were analyzed along their length with Raman microspectroscopy and attenuated total reflection‐Fourier transform infrared micro‐imaging. Both techniques evidenced a different chemical composition in the terminal with respect to the central part of the tendon. Thus, a differentiated analysis was performed depending on the specific position with respect to the bone or the muscle junctions. Spectroscopic analyses showed significant differences in the characteristics of the extracellular matrix between tendons from ECMO and non‐ECMO donors, suggesting changes in the amino acid (proline and hydroxyproline) content and protein structure.
G/ β‐ TCP composite scaffold material promotes osteogenic differentiation of bone marrow mesenchymal stem cells
Authors: Su Hairong , Liao Yong , Yuan Xiaolu , Huang Jianhui , Chen Ya , Zhao Binxiu
Published: August 2023

To explore self‐made graphene/β Graphene (G)/β‐ tricalcium phosphate, G/β‐ The effect of TCP composite scaffold material on osteogenic differentiation of BMSC. Preparation of G/β‐ TCP composite material was used to investigate the effect of composite material on bone marrow mesenchymal stem cell ossification/β‐ TCP material was used to treat primary BMSCs of rats. Cell morphology changes were observed under scanning electron microscopy, cell cycle and proliferation were detected by flow cytometry, and gene expression of chondrogenic genes Fibronectin, collagen I, collagen II, ICAM, and VCAM was detected by q‐PCR. In addition, using osteogenic induction medium and G/β‐ TCP composite materials were co treated with BMSCs, and ALP and alizarin red staining were used to observe the effect of the materials on osteogenic differentiation. q‐PCR was used to detect the gene expression of osteogenic related genes Runx2, OCN, and OPN. G/ β‐ After the TCP composite was co cultured with BMSC, the proportion of G0/G1 phase of BMSC cells was significantly increased, the cell proliferation ability was enhanced, and the gene expression of fibronectin, collagen I, collagen II, ICAM, and VCAM were significantly increased. The ALP staining results indicate that BMSC in G/β‐ After treatment with TCP composite material, significant enhancement of osteogenic ability was observed at 7,14 and 21 days. In addition, BMSC in G/β‐ A significant increase in calcium deposition was observed at 7,14 and 21 days after treatment with TCP composite materials. The effect of different time points on the expression of osteogenic related genes varies. At 7 and 14 days, the expression of RUNX2 was significantly reduced compared to the control, but significantly increased at 21 days; OCN significantly increased on the 21st day; OPN significantly increased at 14 days. G/β‐ TCP materials significantly promote the osteogenic differentiation of BMSCs.
Intraprofessional learning: Dentistry and oral health students’ readiness and experience
Authors: Wong Grace , Irving Michelle , Forsyth Cathryn J. , Chen Rebecca , Tsai Carrie
Published: August 2023

Introduction

Intraprofessional learning is a promising approach to enhance teamwork and patient care. This mixed‐method study aimed to assess the readiness and experience of dental and oral health students toward intraprofessional learning.

Methods

Dental and oral health students were paired alternatively in a clinician and assistant role in a pediatric clinical setting. The Readiness for Interprofessional Learning Scale was adapted for a pre‐ and post‐survey. Focus groups were conducted to elicit the students’ shared learning experience.

Results

Approximately 50% of dental and oral health students participated in the pre‐ and post‐survey. Pre‐test findings revealed similar attitudes toward intraprofessional practice for both groups. However, a statistically significant lower score (p < 0.022) for the oral health students in the post‐test suggested a less positive attitude toward their experience. Qualitative results indicated that dental students acquired a better understanding of the clinical scope of oral health students, and they learned clinical skills and behavior management from their counterparts. Conversely, oral health students experienced a hierarchical lack of collegiality and reciprocity from dental students, which may have contributed to their lower post‐test score. Despite this, some oral health students gained more confidence in their roles and abilities within the intraprofessional team. Overall, dental students valued this learning experience more and desired more intraprofessional opportunities.

Conclusion

Both groups of dental and oral health students had similar readiness levels to enter intraprofessional practice, appreciated the intraprofessional experience, and gained an increased appreciation for the collaborative approach to patient care. Intraprofessional learning during training may assist with developing collegiality across the dental professions in practice.