bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecularly imprinted photonic polymer for rapid visual detection of sulfamethoxazole in environmental water samples
Authors: Nan Jing , Wang Hai‐Qi , Xue Rong‐Chao , Yu Li‐Ping
Published: January 2024

Sulfamethoxazole (SMX) has numerous adverse effects and is present in various water systems; thus, the development of a rapid and accurate analytical method to detect SMX in water systems is crucial for protecting the environment and human health. A sulfamethoxazole molecularly imprinted photonic polymer (MIPP‐SMX) capable of facile naked‐eye recognition of target molecules was synthesized using the dual‐functional monomers acrylamide and methacrylic acid. The color of the MIPP‐SMX changed from green to blue in water samples containing sulfamethoxazole (SMX) in the concentration range of 0.5–5.0 mM. Furthermore, a linear correlation existed between the detected Bragg diffraction peak shift Δλ and SMX concentrations in water ranging from 0.5 to 2.0 mM. The detection limit for SMX was 0.3 mM. A recovery rate of 91.9%–108.5% was achieved when the polymer sensor was used to detect SMX in river water samples, with a relative standard deviation of 4.9%–6.0%. The designed MIPP‐SMX enabled rapid visual detection of SMX in water samples. The proposed method represents a significant advancement in the visual detection of SMX in environmental water samples.
No ageing‐related increase in fibre type grouping in sprint‐trained masters runners: A 10‐year follow‐up study
Authors: Messa Guy Anselme Mpaka , Korhonen Marko T. , Degens Hans
Published: January 2024

Background

Previous research suggests that an ageing‐associated remodelling and loss of motor units due to motor neuron death contributes significantly to muscle weakness in old age. In histological sections, motor unit remodelling is reflected by increased fibre type grouping. While regular exercise may not attenuate the loss of motor units during ageing, it has been suggested to facilitate reinnervation resulting in larger motor units, and a higher number and larger fibre type groups in histological sections of muscles from aged individuals.

Methods

In a 10‐year follow‐up study, we assessed changes in the prevalence and size of fibre type groups in the vastus lateralis muscle from 34 male masters sprinters (40–85 years at start).

Results

Over the 10 years, there was an ageing‐related reduction in performance in the 60‐m sprint (P < 0.001) without significant changes in fibre type composition and fibre cross‐sectional area. Neither the number of fibre type groups, defined as a fibre surrounded exclusively by fibres of the same type, nor the group size changed significantly in the 10‐year period.

Conclusions

These histological data show that there is limited to no significant fibre type grouping over a 10‐year period in masters athletes who continued sprint run training. This observation challenges the paradigm that ageing, at least in systematically trained sprinters, is associated with motor unit remodelling.
Variation in response to the coronavirus disease 2019 (COVID‐19) at US dental school clinics
Authors: Nalliah Romesh P. , Chheda Riddhi , Belgal Priyanka Govind , Kaur Jasmine , Mhay Sahil , Haas Steven , Rowan Susan A
Published: January 2024

Purpose

Although the threat of coronavirus disease 2019 (COVID‐19) was the same at different US dental schools, the response wasn't. There is no study that documents the variation in mitigation strategies, COVID‐19 transmission, and clinical educational changes at US Dental schools during the ongoing pandemic that began in 2020 in the US.

Methods

The current study was approved as exempt research (project number HUM00199261). Our survey of Associate Dean's of Clinical Operations was individually emailed in July 2021. There were no reminders and descriptive statistics were calculated using Microsoft Excel.

Results

We received 46 completed surveys from the 68 sent out. Note that 65.2% of respondents reported requiring N95 masks for aerosol‐generating procedures. Note that 38.9% of respondents said they required student partnering as chairside dental assistants for aerosol‐generating procedures. Note that 37.7% of respondents began using alternate cubicles. A total of 6.52% of schools reported a transmission of the severe acute respiratory syndrome coronavirus 2 virus from patient to provider. There were no reported transmissions from provider to patient or from patient to patient.

Conclusion

In our study, we found a lot of similarities between the approach taken by Dental School Clinics across the US to mitigate the risks of COVID‐19, however, we also observed many differences.
Constructing a personalized prognostic risk model for colorectal cancer using machine learning and multi‐omics approach based on epithelial–mesenchymal transition‐related genes
Authors: Zhang Shuze , Fan Wanli , He Dong
Published: January 2024

The progression and the metastatic potential of colorectal cancer (CRC) are intricately linked to the epithelial–mesenchymal transition (EMT) process. The present study harnesses the power of machine learning combined with multi‐omics data to develop a risk stratification model anchored on EMT‐associated genes. The aim is to facilitate personalized prognostic assessments in CRC. We utilized publicly accessible gene expression datasets to pinpoint EMT‐associated genes, employing a CoxBoost algorithm to sift through these genes for prognostic significance. The resultant model, predicated on gene expression levels, underwent rigorous independent validation across various datasets. Our model demonstrated a robust capacity to segregate CRC patients into distinct high‐ and low‐risk categories, each correlating with markedly different survival probabilities. Notably, the risk score emerged as an independent prognostic indicator for CRC. High‐risk patients were characterized by an immunosuppressive tumor milieu and a heightened responsiveness to certain chemotherapeutic agents, underlining the model's potential in steering tailored oncological therapies. Moreover, our research unearthed a putative repressive interaction between the long non‐coding RNA PVT1 and the EMT‐associated genes TIMP1 and MMP1, offering new insights into the molecular intricacies of CRC. In essence, our research introduces a sophisticated risk model, leveraging machine learning and multi‐omics insights, which accurately prognosticates outcomes for CRC patients, paving the way for more individualized and effective oncological treatment paradigms.
Stability of extemporaneously prepared clofazimine oral suspensions
Authors: Ponsonby‐Thomas Ellie , Lau Charis , Tan Sherine , Salim Malinda , Boyd Ben J.
Published: January 2024

Background

Clofazimine is recommended as a treatment for tuberculosis in infants. Extemporaneously prepared clofazimine oral suspensions are more appropriate dosage forms for infants than tablets, however no data exist to inform appropriate storage conditions.

Aim

To examine the physical and chemical stability of extemporaneously prepared clofazimine oral suspensions and determine appropriate storage conditions.

Method

An oral suspension of clofazimine 10 mg/mL was prepared by grinding six 100 mg clofazimine tablets to produce a fine powder. Ora‐Blend SF (sugar free) was added to make a final volume of 60 mL. Six 10 mL aliquots were placed in amber plastic bottles with plastic bottle caps. Three bottles were stored at room temperature, and three bottles were refrigerated at 4°C. Following shaking, a 1 mL sample was taken from each bottle on days 0, 7, 14, 28, and 60. Samples were assayed using the high‐performance liquid chromatography method. The samples were visually examined for colour change and separation at each time point. Stability was defined as the retention of at least 90% of the initial concentration. Ethics approval was not required for this research article as it was a stability study that did not involve human subjects.

Results

The clofazimine content remained >94% of the initial concentration throughout the 60‐day period for samples that were kept at room temperature, and slightly <90% (87.4%) for samples that were kept refrigerated at 4°C. No separation or colour change was noted throughout the 60‐day period for both preparations.

Conclusion

Extemporaneously prepared suspensions of clofazimine in Ora‐Blend SF were chemically stable for at least 60 days when stored at room temperature. Clofazimine degraded slightly more rapidly at 4°C compared to room temperature.
Moving forward with a culturally inclusive PTSD Criterion A: Commentary on Marx et al. (2023)
Authors: Allwood Maureen A.
Published: January 2024

In response to Marx et al.’s (2023) article, “The PTSD Criterion A debate: A brief history, current status, and recommendations for moving forward,” this commentary offers agreement with the recommendation to conduct population‐based studies to inform future Criterion A changes. However, to fully address the debate as to whether Criterion A should be expanded, limited, eliminated, or remain unchanged, it is critical that future population‐based research focus on cultural inclusivity and the addition of potentially traumatic experiences that are collective and/or cumulative versus individual and discrete. To further understand the etiology of mental health distress and disorder and the role of adverse life experiences, it is also recommended that adverse event specifiers be added to disorders not currently considered to be event‐related. The ability to identify the potential long‐term effects of adverse life experiences in relation to disorders other than posttraumatic stress disorder (e.g., major depressive disorder) could help validate experiences, reduce stigma, and further advance research on etiology and interventions.
Identifying priority mitigation areas for human–osprey conflict
Authors: Murphy Natasha K. , Boudreau Melanie R. , Dorr Brian S. , Slankard Kate , Rush Scott A.
Published: January 2024

Raptor nests on human‐built structures represent a significant source of conflict, as they can result in bird mortality, fires, or power outages due to falling nest materials or animals connecting with energized conductors. Power companies typically try to mitigate these conflicts to avoid service disruptions. Performing mitigation measures across all potentially problematic power infrastructure is generally not a practical solution given logistical, time, or budgetary constraints. Therefore, there is a need for quantitative, landscape‐scale tools to identify conflict risk and prioritize mitigation. We examined the influence of habitat and transmission infrastructure distribution on the potential risk of osprey (Pandion haliaetus) nesting‐infrastructure conflict in the Tennessee Valley Authority (TVA) power service area within Tennessee, Alabama, Georgia, Kentucky, Mississippi, North Carolina, and Virginia, USA, using osprey nesting and conflict records from 1990–2020. We modeled risk using a 3‐stage approach, which intersected a nesting habitat suitability model and density of infrastructure to evaluate the potential risk of conflict. Habitat suitability was greater on or near open water and closer to developed areas. Transmission line density was low (0.14 ± 0.29 lines/km2) and heterogenous across the service area with more lines within urban centers and near power facilities. Integrating habitat suitability and transmission infrastructure information revealed that very low and low‐risk areas comprised 99% of the service area. Less than 1% comprised 1,113.7 km2 of moderate and 82.2 km2 of high or very high risk, mostly concentrated along major rivers and lakes, and around urban centers. Risk was more prevalent in the northeastern portion of the service area. This work presents a top‐down approach to mitigating osprey–power infrastructure conflict, which allows for the prioritization of mitigation actions and can facilitate long‐term coexistence with this protected species.
Trust in Machine Learning Driven Clinical Decision Support Tools Among Otolaryngologists
Authors: Chen Hannah , Ma Xiaoyue , Rives Hal , Serpedin Aisha , Yao Peter , Rameau Anaïs
Published: January 2024

Background

Machine learning driven clinical decision support tools (ML‐CDST) are on the verge of being integrated into clinical settings, including in Otolaryngology‐Head & Neck Surgery. In this study, we investigated whether such CDST may influence otolaryngologists' diagnostic judgement.

Methods

Otolaryngologists were recruited virtually across the United States for this experiment on human–AI interaction. Participants were shown 12 different video‐stroboscopic exams from patients with previously diagnosed laryngopharyngeal reflux or vocal fold paresis and asked to determine the presence of disease. They were then exposed to a random diagnosis purportedly resulting from an ML‐CDST and given the opportunity to revise their diagnosis. The ML‐CDST output was presented with no explanation, a general explanation, or a specific explanation of its logic. The ML‐CDST impact on diagnostic judgement was assessed with McNemar's test.

Results

Forty‐five participants were recruited. When participants reported less confidence (268 observations), they were significantly (p = 0.001) more likely to change their diagnostic judgement after exposure to ML‐CDST output compared to when they reported more confidence (238 observations). Participants were more likely to change their diagnostic judgement when presented with a specific explanation of the CDST logic (p = 0.048).

Conclusions

Our study suggests that otolaryngologists are susceptible to accepting ML‐CDST diagnostic recommendations, especially when less confident. Otolaryngologists' trust in ML‐CDST output is increased when accompanied with a specific explanation of its logic.

Level of Evidence

2 Laryngoscope, 134:2799–2804, 2024
Real‐World Outcomes of Inoperable and Metastatic Cutaneous Head and Neck Melanoma Patients
Authors: Rozendorn Noa , Shutan Itay , Feinmesser Gilad , Grynberg Shirly , Hodadov Hadas , Alon Eran , Asher Nethanel
Published: January 2024

Objective

This study aims to describe the overall survival (OS) and to identify associated prognostic factors in patients with inoperable and metastatic cutaneous melanoma of the head and neck (H&N) region, undergoing modern systemic treatments.

Methods

This is a retrospective single institutional study. Data on all consecutive H&N melanoma patients treated with systemic oncologic treatments between 2015 and 2022 were collected from electronic medical files. Kaplan–Meier curves were used to describe survival and Cox regression analysis was used to identify patient and tumor factors associated with prognosis.

Results

A total of 144 patients were included. Median OS was 45 months (95% confidence interval [CI] 28–65 m). On univariable analysis for OS, the primary disease site, specifically the nape and neck (hazard ratio [HR] 3.3, 95% CI 1.4–7.7, p = 0.007), high Eastern Cooperative Oncology Group Performance Status ([ECOG‐PS], HR 2.5, 95% CI = 1.9–3.3, p < 0.001), high lactate dehydrogenase (LDH) levels (HR 2.8, 95% CI = 1.7–4.6, p < 0.001), and treatment with targeted therapy (TT) as compared with immunotherapy (HR 2.6, 95% CI = 1.06–6.3, p = 0.03) were all associated with shorter OS. High‐grade adverse events (AEs) were associated with a longer OS (HR 0.41, 95% CI = 0.25–0.68, p = 0.001). On multivariable analysis for OS, the ECOG‐PS, LDH levels, site of disease, and the development of moderate‐severe AEs remained significant.

Conclusions

In the era of modern oncologic treatments, the prognosis of inoperable and metastatic cutaneous H&N melanoma aligns with other cutaneous melanomas. Primary tumor site of the nape and neck region emerges as a significant prognostic factor.

Level of Evidence

3 Laryngoscope, 134:2762–2770, 2024
The yardstick approach in a Tullock contest
Authors: Minchuk Yizhaq
Published: January 2024

A contest's organizational structure or mechanism is often determined by the organizer's goal. While most contest organizers are interested in maximizing the effort expended by the contestants, some are interested in maximizing social welfare. We examine the corresponding contest mechanisms using a Tullock contest (standard and winner‐pay) combined with the yardstick approach, which in some cases can achieve both goals simultaneously. Two cases are considered. The first is the yardstick approach that takes the form of a payoff scheme in a standard Tullock contest where the contestants (winners or losers) are reimbursed according to the average effort of the other
contestants. In the second, the yardstick approach is introduced into a winner‐pay contest, in which the winner pays the average cost of the other contestants' efforts.
Norm of the general polynomial differentiation composition operator from the space of Cauchy transforms to the mth weighted‐type space on the unit disk
Authors: Stević Stevo
Published: January 2024

We introduce the general polynomial differentiation composition operator

where
,
,
, are holomorphic functions on the open unit disk
and
,
, are holomorphic self‐maps of
, calculate norm of the operator acting from the space of Cauchy transforms to the
th weighted‐type space, and characterize its boundedness, as well as the boundedness of the operator acting from the space of Cauchy transforms to the little
th weighted‐type space.
vOARiability: Interobserver and intermodality variability analysis in OAR contouring from head and neck CT and MR images
Authors: Podobnik Gašper , Ibragimov Bulat , Peterlin Primož , Strojan Primož , Vrtovec Tomaž
Published: January 2024

Background

Accurate and consistent contouring of organs‐at‐risk (OARs) from medical images is a key step of radiotherapy (RT) cancer treatment planning. Most contouring approaches rely on computed tomography (CT) images, but the integration of complementary magnetic resonance (MR) modality is highly recommended, especially from the perspective of OAR contouring, synthetic CT and MR image generation for MR‐only RT, and MR‐guided RT. Although MR has been recognized as valuable for contouring OARs in the head and neck (HaN) region, the accuracy and consistency of the resulting contours have not been yet objectively evaluated.

Purpose

To analyze the interobserver and intermodality variability in contouring OARs in the HaN region, performed by observers with different level of experience from CT and MR images of the same patients.

Methods

In the final cohort of 27 CT and MR images of the same patients, contours of up to 31 OARs were obtained by a radiation oncology resident (junior observer, JO) and a board‐certified radiation oncologist (senior observer, SO). The resulting contours were then evaluated in terms of interobserver variability, characterized as the agreement among different observers (JO and SO) when contouring OARs in a selected modality (CT or MR), and intermodality variability, characterized as the agreement among different modalities (CT and MR) when OARs were contoured by a selected observer (JO or SO), both by the Dice coefficient (DC) and 95‐percentile Hausdorff distance (HD ).

Results

The mean (±standard deviation) interobserver variability was 69.0 ± 20.2% and 5.1 ± 4.1 mm, while the mean intermodality variability was 61.6 ± 19.0% and 6.1 ± 4.3 mm in terms of DC and HD , respectively, across all OARs. Statistically significant differences were only found for specific OARs. The performed MR to CT image registration resulted in a mean target registration error of 1.7 ± 0.5 mm, which was considered as valid for the analysis of intermodality variability.

Conclusions

The contouring variability was, in general, similar for both image modalities, and experience did not considerably affect the contouring performance. However, the results indicate that an OAR is difficult to contour regardless of whether it is contoured in the CT or MR image, and that observer experience may be an important factor for OARs that are deemed difficult to contour. Several of the differences in the resulting variability can be also attributed to adherence to guidelines, especially for OARs with poor visibility or without distinctive boundaries in either CT or MR images. Although considerable contouring differences were observed for specific OARs, it can be concluded that almost all OARs can be contoured with a similar degree of variability in either the CT or MR modality, which works in favor of MR images from the perspective of MR‐only and MR‐guided RT.
Ontological Collisions in the Northern Territory's Aboriginal Water Rights Policy
Authors: Jackson Sue , O'Donnell Erin , Godden Lee , Langton Marcia
Published: January 2024

Amid a renewed push to extract water for agriculture and mining, Indigenous advocacy in northern Australia has resulted in the introduction of a new water allocation mechanism: a reserve of water to be retained for the use and benefit of Indigenous communities. Our socio‐legal analysis of the Oolloo Water Allocation Plan shows that the Strategic Aboriginal Water Reserves carry essential hallmarks of neoliberal property relations and are founded in the modernist mode of regulating extracted water as a commodity divisible from land, amenable to partitioning and disarticulated from socio‐cultural relations. Informed by ethnographic material from the Daly River region gathered over almost a century, we describe the hydro‐social relations that are created through customary traditions and practices, water planning and licencing, and the interaction between different scales of water movement and decision‐making by both the state and Traditional Owners. The paper contributes in several ways to research that has identified ontological conflicts as central to disagreements over water and pointed to the difficulty of articulating theoretical framings of ontological difference with the practical work of water negotiations. It shows how the new Indigenous water rights discourse that coincided with the commodification of water in wider Australia shaped the way in which Aboriginal people of this region have more recently articulated their relationships to the Daly River and the limits to state recognition of those relationships. We find that the Reserve model is unable to recognize the capacity of water to connect and unify people and other beings, as well as to define boundaries between them. Within a regime that facilitates resource extraction, a limited opening has been created for Aboriginal people to benefit from this model of economic development, yet we argue that there is reason to fear that the divisions the Aboriginal Water Reserve enacts between waters and land presents significant socio‐cultural risks.
FANCD2 deficiency sensitizes SHH medulloblastoma to radiotherapy via ferroptosis
Authors: Zhou Hong , Wang Yan‐Xia , Wu Min , Lan Xi , Xiang Dongfang , Cai Ruili , Ma Qinghua , Miao Jingya , Fang Xuanyu , Wang Junjie , Luo Dan , He Zhicheng , Cui Youhong , Liang Ping , Wang Yan , Bian Xiu‐Wu
Published: January 2024

Radiotherapy is one of the standard therapeutic regimens for medulloblastoma (MB). Tumor cells utilize DNA damage repair (DDR) mechanisms to survive and develop resistance during radiotherapy. It has been found that targeting DDR sensitizes tumor cells to radiotherapy in several types of cancer, but whether and how DDR pathways are involved in the MB radiotherapy response remain to be determined. Single‐cell RNA sequencing was carried out on 38 MB tissues, followed by expression enrichment assays. Fanconi anemia group D2 gene (FANCD2) expression was evaluated in MB samples and public MB databases. The function of FANCD2 in MB cells was examined using cell counting assays (CCK‐8), clone formation, lactate dehydrogenase activity, and in mouse orthotopic models. The FANCD2‐related signaling pathway was investigated using assays of peroxidation, a malondialdehyde assay, a reduced glutathione assay, and using FerroOrange to assess intracellular iron ions (Fe2+). Here, we report that FANCD2 was highly expressed in the malignant sonic hedgehog (SHH) MB subtype (SHH‐MB). FANCD2 played an oncogenic role and predicted worse prognosis in SHH‐MB patients. Moreover, FANCD2 knockdown markedly suppressed viability, mobility, and growth of SHH‐MB cells and sensitized SHH‐MB cells to irradiation. Mechanistically, FANCD2 deficiency led to an accumulation of Fe2+ due to increased divalent metal transporter 1 expression and impaired glutathione peroxidase 4 activity, which further activated ferroptosis and reduced proliferation of SHH‐MB cells. Using an orthotopic mouse model, we observed that radiotherapy combined with silencing FANCD2 significantly inhibited the growth of SHH‐MB cell‐derived tumors in vivo. Our study revealed FANCD2 as a potential therapeutic target in SHH‐MB and silencing FANCD2 could sensitize SHH‐MB cells to radiotherapy via inducing ferroptosis. © 2024 The Pathological Society of Great Britain and Ireland.
N‐methylmorpholine‐N‐oxide molecules coated ammonium polyphosphates for dope spinning of flame‐retardant lyocell fiber
Authors: Bai Shuyu , Peng Junwu , Nie Ling , Liu Xinglin , Liang Yaoting , Zhu Zongmin , Zhu Kunkun
Published: January 2024

Lyocell fiber, hailed as the “verdant filament of the 21st century,” boasts elevated tensile strength, environmentally conscientious production practices, and innate biodegradability. Nonetheless, its intrinsic combustibility constitutes a noteworthy impediment to its pervasive utilization across textile and industrial domains. In a concerted effort to surmount this challenge, ammonium polyphosphate (APP) underwent modification through the infusion of N‐methylmorpholine‐N‐oxide (NMMO) molecules, amplifying its dispersibility within lyocell solutions. The resultant NMMO‐coated ammonium polyphosphate (NAPP) underwent meticulous characterization of both its structure and properties. Remarkably, lyocell fiber impregnated with 30% NAPP exhibited exemplary flame retardancy, enduring through 30 laundering cycles. Notably, its tensile strength remained notably robust at 139 MPa, demonstrating a mere 6.1% reduction in comparison to its pristine lyocell counterpart. This study delineates a promising trajectory for the fabrication of mechanically resilient lyocell fibers endowed with commendable flame‐retardant attributes.

Highlights

The raw material is waste cotton textiles, prepared on a green basis.

The use of ultrasonic mixing and low‐speed stirring defoaming method and the use of room temperature spinning advantage of the production of flame retardant lyocell fiber.

The amount of flame retardant is small, and the mechanical strength is reduced to a lesser extent.

Good flame‐retardant effect and excellent water washing resistance.
Fracture assessment of inclined double keyhole notches in polylactic acid specimens fabricated by fused deposition modeling and traditional method
Authors: Fateri Mohammad Taghi , Kordani Naser , Salavati Hadi , Mohammadi Abokheili Rasool
Published: January 2024

The fracture behavior of specimens made of polylactic acid and weakened by inclined double keyhole notches is investigated by both experimental and numerical methods. The test specimens are fabricated by two different methods; fused deposition modeling and traditional methods. The mechanical behavior of specimens was investigated under mixed‐mode loading with different notch inclination angles, various notch tip radius, and multiple raster angles. An experimental program was performed, and 72 new experimental data were provided. A fracture criterion based on the strain energy density is used to assess the critical fracture loads of the tested specimens. Good agreement is found between experimental and numerical data. The results showed that increasing the notch inclination angle and notch tip radius led to a decrease in the fracture load of the specimens. Also, fracture loads of the classical specimens are higher than the 3D‐printed specimens. In the 3D‐printed specimens, fracture loads for the samples with raster angles of 0°, 45°, and 90° have the highest value, respectively.

Highlights

Fracture assessment of polylactic acid specimens

Specimens were weakened by using an eccentric inclined double keyhole notch

Specimens manufactured by fused deposition modeling and traditional method

Investigation of different notch inclination angles and notch tip radius

Evaluation of specimens using experimental and numerical analysis methods
Synthesis of well‐defined aromatic poly(amide‐ether)s via chain‐growth condensation polymerization
Authors: Dickhudt Rhys J. , Devineni Geetesh , Kostal Jakub , Boyes Stephen G.
Published: January 2024

Since their advent over 50 years ago, aromatic polyamides have remained desirable for their thermal stability, mechanical strength, and overall versatility. Chain‐growth condensation (CGC) polymerization has made possible the synthesis of well‐defined polyamides with narrow molecular weight distributions for applications ranging from block copolymers to polymer brushes. However, the solubility of aromatic polyamides has always been a major obstacle to overcome due to aromatic π‐π stacking and intramolecular hydrogen bonding. In this article, we introduce an aryl ether functionality into the polyamide backbone to increase backbone flexibility and overall solubility. Through dropwise addition of the aryl ether functionalized monomer with a lithium disilazide base and a phenyl 4‐(dimethylcarbamoyl)benzoate initiator, we report the synthesis of a series of substituted poly(amide‐ether)s through CGC polymerization with low polydispersities (<1.1) and well‐defined molecular weights. Computational methods revealed that the polymerization mechanism is unlike other similar amino ester monomers bearing naphthalene and biphenyl aromatic units in that monomer self‐deactivation is weakened by the ether linkage. The self‐condensation of the amide‐ether monomer was nevertheless suppressed through reaction optimization, challenging the traditional requirement of monomer self‐deactivation to achieve a well‐defined CGC polymerization. The side‐chain on poly(amide‐ether) backbone was also modified from an octyl group to a 4‐(octyloxy)benzyl protecting group for postpolymerization removal with trifluoroacetic acid to yield the unsubstituted aromatic poly(amide‐ether), which showed a significant improvement in solubility from traditional unsubstituted aromatic polyamides, such as poly(p‐benzamide).
LC/Q‐TOF‐MS‐based structural characterization of enasidenib degradation products and establishment of a stability‐indicating assay method: Insights into chemical stability
Authors: Chakkar Avinash , Chaturvedi Sachin , Rajput Niraj , Sengupta Pinaki , Sharma Nitish
Published: January 2024

Rationale

Enasidenib (EDB) is an orally active selective mutant isocitrate dehydrogenase‐2 enzyme inhibitor approved by the U.S. Food and Drug Administration to treat acute myeloid leukemia. It lacks a reported forced degradation study and a stability‐indicating assay method (SIAM). This study addresses this gap by establishing a degradation profile in accordance with the International Council for Harmonisation Q1A and Q1B (R2) guidelines and developing a validated SIAM for EDB.

Methods

EDB was exposed to forced degradation under various conditions (hydrolytic, photolytic, oxidative, and thermal stress). Degradation samples were analyzed using high‐performance liquid chromatography on an Agilent ZORBAX Eclipse Plus C18 column with a mobile phase consisting of 0.1% formic acid in Milli‐Q water and acetonitrile at a flow rate of 1 mL/min and detection at 270 nm. Liquid chromatography‐quadrupole time‐of‐flight‐high‐resolution mass spectrometry (LC/Q‐TOF HRMS) was used for the identification and characterization of degradation products. Nitrosamine risk assessment was conducted using a modified nitrosation assay procedure (NAP) test due to the presence of a secondary amine group in the drug, which is liable to forming nitrosamine drug substance–related impurities (NDSRI).

Results

The drug exhibited significant degradation under acidic, basic, photolytic, and oxidative conditions in the solution state. A total of nine degradation products (DP) were formed (DP‐I, DP‐III, and DP‐IV: acidic conditions; DP‐I and DP‐III: basic conditions; DP‐II, DP‐V, DP‐VI, and DP‐VII: oxidative stress; and DP‐VII, DP‐VIII, and DP‐IX: photolytic conditions), which were separated and identified using reversed‐phase high‐performance liquid chromatography and characterized using liquid chromatography–tandem mass spectrometry. The mechanism behind the formation of EDB degradation products has been discussed, and this study was the first to develop a degradation pathway for EDB. In addition, the possibilities of NDSRI formation for EDB were studied using a modified NAP test, which can contribute to the risk assessment of the drug.

Conclusions

Forced degradation studies were conducted by establishing a SIAM for EDB. All the degradation products were characterized by mass spectral data obtained using LC/Q‐TOF‐HRMS.
Establishment of high‐performance liquid chromatography‐photodiode array method for 43 weight loss agents and effect of basic environment on bisacodyl degradation
Authors: Lee Ji Hyun , Ham Hyeon Joo , Bae Hye‐Min , Han Kyoung‐Moon , Lee Jongkook , Kim Hyung Il
Published: January 2024

Rationale

The demand for weight loss products is increasing as slimness emerges as the new aesthetic standard and people's desire to achieve it increases. In addition, the distribution and sale of products containing illegal ingredients, pharmaceuticals, and chemicals for which safety is not guaranteed and that cannot be used as foods or dietary supplements are increasing. Thus, the development of an analytical method that could monitor these illegal products is required.

Methods

A high‐performance liquid chromatography‐photodiode array method capable of rapid and reliable qualitative and quantitative analyses of 43 weight loss agents was established and validated.

Results

The process involved dividing analytes into three groups for rapid analysis; when bisacodyl was mixed with chlorocyclopentylsibutramine, it decomposed into its metabolites: monoacetyl bisacodyl and bis‐(p‐hydroxypheny)‐pyridyl‐2‐methane. This decomposition was due to NaOH that was used to prepare the chlorocyclopentylsibutramine standard solution. Bisacodyl did not degrade when mixed with neutralized chlorocyclopentylsibutramine, whereas when NaOH was added, it rapidly degraded. We identified the bisacodyl degradation products using liquid chromatography‐quadrupole‐Orbitrap/mass spectrometry. MS2 spectra with proposed structures of fragment peaks were also obtained.

Conclusions

The developed method could be used to regulate slimming products that threaten public health, and knowledge of bisacodyl degradation will be used as the basis for developing an analytic method.
Inclusive education, gender inequality and public expenditure in sub‐Saharan Africa
Authors: Mbodji Yérim Codé
Published: January 2024

In the contemporary literature, several studies have attempted to see the effect of gender inequality and public expenditure on inclusive education. However, few have attempted to determine the gender inequality threshold. In this study, we first examined the threshold of gender inequality which, when exceeded, the effect on inclusive education becomes negative. Second, we examined the effect of public expenditure on inclusive education in 17 countries in sub‐Saharan Africa, in the period from 2000 to 2019. The fixed‐effect panel data model was used. The following results have been established: (i) the gender inequality threshold from which the effect of gender inequality becomes negative on the gross enrolment rate is respectively established at 0.38 in primary and 0.37 in secondary. At the higher level, the effect of gender inequality is linear and negative on the gross enrolment rate; (ii) public expenditure on education has a positive and significant effect at the primary and secondary level on inclusive education. However, its effect at the higher level is negative. As implications, the results constitute and intermediate objective for the countries for the sub‐Saharan Africa which failing to achieve gender equality, would benefit from reducing inequality to 0.38 at primary level and 0.37 at secondary level. Secondary, education in order to cancel out the negative effect of gender inequality on gross enrolment rates at the primary and secondary level. Secondly, states must further consider public education expenditure as a relevant instrument for achieving SDG 4.
Controlled descent training
Authors: Andersson Viktor , Varga Balázs , Szolnoky Vincent , Syrén Andreas , Jörnsten Rebecka , Kulcsár Balázs
Published: January 2024

In this work, a novel and model‐based artificial neural network (ANN) training method is developed supported by optimal control theory. The method augments training labels in order to robustly guarantee training loss convergence and improve training convergence rate. Dynamic label augmentation is proposed within the framework of gradient descent training where the convergence of training loss is controlled. First, we capture the training behavior with the help of empirical Neural Tangent Kernels (NTK) and borrow tools from systems and control theory to analyze both the local and global training dynamics (e.g., stability, reachability). Second, we propose to dynamically alter the gradient descent training mechanism via fictitious labels as control inputs and an optimal state feedback policy. In this way, we enforce locally optimal and convergent training behavior. The novel algorithm, Controlled Descent Training (CDT), guarantees local convergence. CDT unleashes new potentials in the analysis, interpretation, and design of ANN architectures. The applicability of the method is demonstrated on standard regression and classification problems.
A Strategy for Enhancing Perpendicular Magnetic Anisotropy in Yttrium Iron Garnet Films
Authors: Meng Ying , Chen Peng , He Wenqing , Zhuang Haoyu , Li Jiahui , Dong Jing , Li Xiangfei , Wang Luyao , Guo Qinwen , Yang Junkai , Ji Yu , Shen Xi , Yu Xiaohui , Yu Guoqiang , Li Junjie , Han Xiufeng , Yu Richeng
Published: January 2024

In future information storage and processing, magnonics is one of the most promising candidates to replace traditional microelectronics. Yttrium iron garnet (YIG) films with perpendicular magnetic anisotropy (PMA) have aroused widespread interest in magnonics. Obtaining strong PMA in a thick YIG film with a small lattice mismatch (η) has been fascinating but challenging. Here, a novel strategy is proposed to reduce the required minimum strain value for producing PMA and increase the maximum thickness for maintaining PMA in YIG films by slight oxygen deficiency. Strong PMA is achieved in the YIG film with an η of only 0.4% and a film thickness up to 60 nm, representing the strongest PMA for such a small η reported so far. Combining transmission electron microscopy analyses, magnetic measurements, and a theoretical model, it is demonstrated that the enhancement of PMA physically originates from the reduction of saturation magnetization and the increase of magnetostriction coefficient induced by oxygen deficiency. The Gilbert damping values of the 60‐nm‐thick YIG films with PMA are on the order of 10−4. This strategy improves the flexibility for the practical applications of YIG‐based magnonic devices and provides promising insights for the theoretical understanding and the experimental enhancement of PMA in garnet films.
Small Warriors of Nature: Novel Red Emissive Chlorophyllin Carbon Dots Harnessing Fenton‐Fueled Ferroptosis for In Vitro and In Vivo Cancer Treatment
Authors: Kirbas Cilingir Emel , Besbinar Omur , Giro Linda , Bartoli Mattia , Hueso Jose L. , Mintz Keenan J. , Aydogan Yagmur , Garber Jordan M. , Turktas Mine , Ekim Okan , Ceylan Ahmet , Unal Mehmet Altay , Ensoy Mine , Arı Fikret , Ozgenç Çinar Ozge , Ozturk Berfin Ilayda , Gokce Cemile , Cansaran‐Duman Demet , Braun Markus , Wachtveitl Josef , Santamaria Jesus , Delogu Lucia Gemma , Tagliaferro Alberto , Yilmazer Açelya , Leblanc Roger M.
Published: January 2024

The appeal of carbon dots (CDs) has grown recently, due to their established biocompatibility, adjustable photoluminescence properties, and excellent water solubility. For the first time in the literature, copper chlorophyllin‐based carbon dots (Chl‐D CDs) are successfully synthesized. Chl‐D CDs exhibit unique spectroscopic traits and are found to induce a Fenton‐like reaction, augmenting photodynamic therapy (PDT) efficacies via ferroptotic and apoptotic pathways. To bolster the therapeutic impact of Chl‐D CDs, a widely used cancer drug, temozolomide, is linked to their surface, yielding a synergistic effect with PDT and chemotherapy. Chl‐D CDs' biocompatibility in immune cells and in vivo models showed great clinical potential.Proteomic analysis was conducted to understand Chl‐D CDs' underlying cancer treatment mechanism. The study underscores the role of reactive oxygen species formation and pointed toward various oxidative stress modulators like aldolase A (ALDOA), aldolase C (ALDOC), aldehyde dehydrogenase 1B1 (ALDH1B1), transaldolase 1 (TALDO1), and transketolase (TKT), offering a deeper understanding of the Chl‐D CDs' anticancer activity. Notably, the Chl‐D CDs' capacity to trigger a Fenton‐like reaction leads to enhanced PDT efficiencies through ferroptotic and apoptotic pathways. Hence, it is firmly believed that the inherent attributes of Chl‐CDs can lead to a secure and efficient combined cancer therapy.
Protein‐Assisted Large‐Scale Assembly and Differential Patterning of DNA Origami Lattices
Authors: Gavrilović Svetozar , Brüggenthies Gereon Andreas , Weck Johann Moritz , Heuer‐Jungemann Amelie , Schwille Petra
Published: January 2024

Nanofabrication has experienced a big boost with the invention of DNA origami, enabling the production and assembly of complex nanoscale structures that may be able to unlock fully new functionalities in biology and beyond. The remarkable precision with which these structures can be designed and produced is, however, not yet matched by their assembly dynamics, which can be extremely slow, particularly when attached to biological templates, such as membranes. Here, the rapid and controlled formation of DNA origami lattices on the scale of hundreds of micrometers in as little as 30 minutes is demonstrated, utilizing active patterning by the E.coli Min protein system, thereby yielding a remarkable improvement over conventional passive diffusion‐based assembly methods. Various patterns, including spots, inverse spots, mazes, and meshes can be produced at different scales, tailored through the shape and density of the assembled structures. The differential positioning accomplished by Min‐induced diffusiophoresis even allows the introduction of “pseudo‐colors”, i.e., complex core–shell patterns, by simultaneously patterning different DNA origami species. Beyond the targeted functionalization of biological surfaces, this approach may also be promising for applications in plasmonics, catalysis, and molecular sensing.
Hydrogen‐Bonded Cocrystals Encapsulating CsPbBr3 Perovskite Nanocrystals with Enhancement of Charge Transport for Photocatalytic Reduction of Uranium
Authors: Cai Yuan‐Jun , Luo Qiu‐Xia , Jiang Qiao‐Qiao , Liu Xin , Chen Xiao‐Juan , Liu Jin‐Lan , Mao Xiang‐Lan , Qi Jia‐Xin , Liang Ru‐Ping , Qiu Jian‐Ding
Published: January 2024

At present, poor stability and carrier transfer efficiency are the main problems that limit the development of perovskite‐based photoelectric technologies. In this work, hydrogen‐bonded cocrystal‐coated perovskite composite (PeNCs@NHS‐M) is easily obtained by inducing rapid crystallization of melamine (M) and N‐hydroxysuccinimide (NHS) with PeNCs as the nuclei. The outer NHS‐M cocrystal passivates the undercoordinated lead atoms by forming covalent bonds, thereby greatly reducing the trap density while maintaining good structure stability for perovskite nanocrystals. Moreover, benefiting from the interfacial covalent band linkage and long‐range ordered structures of cocrystals, the charge transfer efficiency is effectively enhanced and PeNCs@NHS−M displays superior photoelectric performance. Based on the excellent photoelectric performance and abundant active sites of PeNCs@NHS−M, photocatalytic reduction of uranium is realized. PeNCs@NHS−M exhibits U(VI) reduction removal capability of up to 810.1 mg g−1 in the presence of light. The strategy of cocrystals trapping perovskite nanocrystals provides a simple synthesis method for composites and opens up a new idea for simultaneously improving the stability and photovoltaic performance of perovskite.
Self‐Assembled DNA Nanospheres Driven by Carbon Dots for MicroRNAs Imaging in Tumor via Logic Circuit
Authors: Chen Qiutong , Xia Xinyi , Liang Zhigang , Zuo Tongshan , Xu Guanhong , Wei Fangdi , Yang Jing , Hu Qin , Zhao Zheng , Tang Ben Zhong , Cen Yao
Published: January 2024

DNA nanostructures with diverse biological functions have made significant advancements in biomedical applications. However, a universal strategy for the efficient production of DNA nanostructures is still lacking. In this work, a facile and mild method is presented for self‐assembling polyethylenimine‐modified carbon dots (PEI‐CDs) and DNA into nanospheres called CANs at room temperature. This makes CANs universally applicable to multiple biological applications involving various types of DNA. Due to the ultra‐small size and strong cationic charge of PEI‐CDs, CANs exhibit a dense structure with high loading capacity for encapsulated DNA while providing excellent stability by protecting DNA from enzymatic hydrolysis. Additionally, Mg2+ is incorporated into CANs to form Mg@CANs which enriches the performance of CANs and enables subsequent biological imaging applications by providing exogenous Mg2+. Especially, a DNAzyme logic gate system that contains AND and OR Mg@CANs is constructed and successfully delivered to tumor cells in vitro and in vivo. They can be specifically activated by endogenic human apurinic/apyrimidinic endonuclease 1 and recognize the expression levels of miRNA‐21 and miRNA‐155 at tumor sites by logic biocomputing. A versatile pattern for delivery of diverse DNA and flexible logic circuits for multiple miRNAs imaging are developed.
Exploring Non‐Toxic Lower Dimensional Perovskites for Next‐Generation X‐Ray Detectors
Authors: Ali Nasir , Shehzad Khurram , Attique Sanam , Ali Ayaz , Akram Fazli , Younis Adnan , Ali Shahid , Sun Yan , Yu Guolin , Wu Huizhen , Dai Ning
Published: January 2024

Owing to their extraordinary photophysical properties, organometal halide perovskites are emerging as a new material class for X‐ray detection. However, the existence of toxic lead makes their commercialization questionable and should readily be replaced. Accordingly, several lead alternatives have been introduced into the framework of conventional perovskites, resulting in various new perovskite dimensionalities. Among these, Pb‐free lower dimensional perovskites (LPVKs) not only show promising X‐ray detecting properties due to their higher ionic migration energy, wider and tunable energy bandgap, smaller dark currents, and structural versatility but also exhibit extended environmental stability. Herein, first, the structural organization of the PVKs (including LPVKs) is summarized. In the context of X‐ray detectors (XDs), the outstanding properties of the LPVKs and active layer synthesis routes are elaborated afterward. Subsequently, their applications in direct XDs are extensively discussed and the device performance, in terms of the synthesis method, device architecture, active layer size, figure of merits, and device stability are tabulated. Finally, the review is concluded with an in‐depth outlook, thoroughly exploring the present challenges to LPVKs XDs, proposing innovative solutions, and future directions. This review provides valuable insights into optimizing non‐toxic Pb‐free perovskite XDs, paving the way for future advancements in the field.