bluuebunny/crossref_metadata_2025 huggingface dataset:
Can We Read Cosmology in Ancient Maya City Plans? Comment on Ashmore and Sabloff
Authors: Smith Michael E.
Published: February 2007

Arguments for the cosmological significance of ancient Maya city layouts are plausible, but empirical applications are subjective and lack rigor. I illustrate this contention through brief comments on a recent article by Ashmore and Sabloff. I first discuss some of the complexities and pitfalls in studying cosmology from ancient city plans, and then focus on one component of the authors’ cosmological model—the hypothesized north-south axis at Classic Maya cities. My goal is not to down-play or rule out the role of cosmology in Maya city planning, but rather to encourage the use of explicit assumptions and rigorous methods that will provide the study of Maya city planning with a more secure empirical foundation.
Spatial Negotiations in a Commercial City: The Red Sea Port of Mocha, Yemen, during the First Half of the Eighteenth Century
Authors: Um Nancy
Published: February 2007

The city of Mocha in Yemen was one of the most important Red Sea ports of the early modern Arab world. In this essay, I examine the urban structures that governed the needs and practices of merchants in the city during the first half of the eighteenth century. Drawing on contemporary Arabic chronicles, archival European trade documents, historical photographs, and fieldwork in the city, I document the conspicuous absence of a network of public trade structures, like the urban khan, the expected locus of trade in an Arab city devoted to international commerce, and I provide evidence of the use of the merchant's house as the central location for trade activity, commercial negotiations, storage of merchandise, and lodging of foreign merchants. This case study presents a form of commercial interaction that questions a fixed private identity for the house in Mocha and draws on a maritime system of interaction to account for such a unique form of trade in an Arab city that served as an important Indian Ocean port.
Reconstituting Chinese Building Tradition: The Yingzao fashi in the Early Twentieth Century
Authors: Shiqiao Li
Published: February 2007

In this paper, I analyze several early-twentieth-century attempts to reprint, edit, and annotate a Northern Song dynasty (960-1127) construction manual, the Yingzao fashi (1103), each one revealing an aspect of the project to define Chinese architecture. As manifested in the research on the Yingzao fashi by a number of Chinese scholars and architects, the project to reconstitute and understand the text was closely connected to broader intellectual issues in early-twentieth-century China: nationalism, philological scholarship, and modern historiography. The Yingzao fashi was rediscovered in 1919 by politician and scholar Zhu Qiqian, who saw it as an important text that provided crucial knowledge of the tradition of Chinese architecture. It also became a central document in the construction of a modern Chinese architectural history by Liang Sicheng, Lin Huiyin, and Liu Dunzhen, which was founded on a historiography strongly influenced by the European Enlightenment tradition. Interest in the Yingzao fashi declined in the latter half of the twentieth century due to a Communist cultural policy germinated at Yan'an in the 1940s. The reappearance of the Yingzao fashi in the early twentieth century played a much broader intellectual role than the book originally had as a manual of construction and administration.
The Linear Plan for Insane Asylums in the United States before 1866
Authors: Yanni Carla
Published: February 2007

Nineteenth-century psychiatrists believed that 80 percent of insanity cases were curable if treated early, outside the home, in carefully planned, purpose-built structures. This essay traces the development of the architecture of insane asylums in the United States. In 1854, the Quaker Philadelphian Thomas S. Kirkbride published guidelines for 250-bed asylums; they were based in part on John Notman's state hospital in Trenton, New Jersey, and dominated asylum design for decades. While followers of Kirkbride favored large aggregate buildings, other reformers supported the cottage plan, a system that broke the monolithic hospitals into small, houselike edifices. Although the doctors disagreed on many issues, they concurred that the architecture of asylums was one of the most powerful tools for the treatment of insanity. Additionally, the paper explores a concept that architectural historians and architects sometimes take for granted: that architecture shapes behavior. In this case, it was expected to help cure a disease.
"Some Imperial Institute": Architecture, Symbolism, and the Ideal of Empire in Late Victorian Britain, 1887-93
Authors: Bremner G. Alex
Published: February 2007

This article explores the relationship between architecture and imperial idealism in late Victorian Britain. It traces the development of the Imperial Institute in the South Kensington section of London from conception to completion, considering the proposals that surrounded the scheme in relation to the sociopolitical context within which it emerged. Sources such as letters, guidebooks, newspapers, journal articles, official publications, and government documents are drawn upon; from them an interpretation of the building is offered that moves beyond issues concerning style and patronage to broader cultural implications. The institute evolved as a consequence of the changing circumstances then affecting British foreign and imperial affairs, and commonly held beliefs relating to empire were reflected in the building's architecture. Analysis of the leading ideas that shaped the scheme formally and spatially reveals that the edifice was intended to stand literally as an emblem of the apparent strength and unity of the British empire. The importance of the institute as an architectural idea, therefore, lies not only in its attempt to give symbolic form to a concept of empire that was at the heart of late Victorian concerns, but also in the way it sought to mark and distinguish London as the center and capital of that empire.
Immunohistochemical evaluation of cyclooxygenase expression in corneal squamous cell carcinoma in horses
Authors: McInnis Carey L. , Giuliano Elizabeth A. , Johnson Philip J. , Turk James R.
Published: February 2007

Objective—To evaluate expression of cyclooxygenase (COX)-1 and COX-2 in the cornea, eyelid, and third eyelid of healthy horses and those affected with squamous cell carcinoma (SCC) by use of immunohistochemical techniques.

Animals—15 horses with SCC involving ocular tissues and 5 unaffected control horses.

Procedures—SCC-affected tissues were obtained from the cornea (n = 5 horses), eyelid (5), and third eyelid (5). Site-matched control tissues were obtained from 5 horses unaffected with SCC. Tissue sections of affected and control cornea, eyelid, and third eyelid were stained immunohistochemically for COX-1 and COX-2 via standard techniques. Stain uptake was quantified by use of computer-assisted image analysis of digital photomicrographs.

Results—Immunoreactivity for both COX-1 and COX-2 was significantly greater in equine corneas with SCC than in control corneas. No significant differences in COX-1 or COX-2 immunoreactivity were detected in eyelid and third-eyelid SCC, compared with site-matched control tissues.

Conclusions and Clinical Relevance—Immunoreactivity for COX-1 and COX-2 is high in equine corneal SCC, possibly indicating that COX plays a role in oncogenesis or progression of this tumor type at this site. Pharmacologic inhibition of COX may represent a useful adjunctive treatment for corneal SCC in horses.
Treatment of traumatic cervical myelopathy with surgery, prolonged positive-pressure ventilation, and physical therapy in a dog
Authors: Smarick Sean D. , Rylander Helena , Burkitt Jamie M. , Scott Nancy E. , Woelz Jacqueline S. , Jandrey Karl E. , Aldrich Janet , Sturges Beverly K.
Published: February 2007

Case Description—A 9-year-old dog was evaluated for traumatic cervical myelopathy after a surgical attempt to realign and stabilize the C2 and C3 vertebrae.

Clinical Findings—The dog could not ventilate spontaneously and was tetraplegic; positive-pressure ventilation (PPV) was maintained. Myelography and computed tomography revealed spinal cord compression with subluxation of the C2 and C3 vertebrae and extrusion of the C2-3 intervertebral disk.

Treatment and Outcome—Surgically, the protruding disk material was removed and the vertebrae were realigned with screws and wire. For PPV, assist control ventilation in volume control mode and then in pressure control mode was used in the first 6 days; this was followed by synchronized intermittent mandatory ventilation until 33 days after the injury; then only continuous positive airway pressure was provided until the dog could breathe unassisted, 37 days after the injury. Physical therapy that included passive range of motion exercises, neuromuscular electrical stimulation, and functional weight-bearing positions was administered until the dog was discharged 46 days after injury; the dog was severely ataxic and tetraparetic but could walk. Therapy was continued at home, and 1 year later, the dog could run and had moderate ataxia and tetraparesis.

Clinical Relevance—Hypoventilation with tetraparesis in traumatic spinal cord injury can be successfully treated with PPV exceeding 30 days, surgery, and physical therapy.
Ultrasound-assisted collection of cerebrospinal fluid from the lumbosacral space in equids
Authors: Aleman Monica , Borchers Angela , Kass Philip H. , Puchalski Sarah M.
Published: February 2007

Objective—To describe ultrasonographic landmarks for use in collection of CSF from the lumbosacral region in equids.

Design—Prospective study.

Animals—37 equids (27 with neurologic disease and 10 with nonneurologic disease).

Procedures—Standing equids (n = 17) were sedated with detomidine hydrochloride (0.006 to 0.01 mg/kg [0.003 to 0.005 mg/lb], IV) followed by butorphanol tartrate (0.01 mg/kg, IV) and restrained with a nose twitch for collection of CSF. The CSF was collected from 20 laterally recumbent equids (10 sedated and 10 immediately after euthanasia). Anatomic landmarks were identified ultrasonographically. Height at the dorsal point of the shoulders, body weight, depth of the spinal needle, number of attempts to collect CSF, and cytologic evaluation of CSF were recorded.

Results—Lumbosacral puncture cranial to the cranial border of the most superficial location of both tuber sacrale along the midline was consistently successful for CSF collection (35/37 equids). Two horses had anatomic abnormalities that precluded CSF collection. Mean number of attempts to collect CSF per animal was 1.1. Height and body weight were strongly correlated with needle depth for CSF collection. Pelvic and sacral displacement was observed in several laterally recumbent animals, which resulted in discrepancies of the midline between the cranial and caudal aspects of the vertebral column. In most equids, the spinal needle was aligned on the midline of the caudal aspect of the vertebral column.

Conclusions and Clinical Relevance—Ultrasonography was a useful aid for collection of CSF from the lumbosacral space and decreased the risk of repeated trauma and contamination in equids.
Operative Management of Ankle Fractures in Patients with Diabetes Mellitus
Authors: Costigan William , Thordarson David B. , Debnath Ujjwal K.
Published: February 2007

Background: Multiple studies have documented increased risks associated with treatment of ankle fractures in patients with diabetes mellitus. We reviewed our results in the largest series to date of this complex patient group to determine the frequency of complications. Methods: Eighty-four patients with diabetes had open reduction and internal fixation using standard fixation techniques for acute, closed ankle fractures. The 51 men and 33 women had an average age was 49.3 (22 to 77) years. The average followup was 4.1 years (11 to 97 months). Seventy-five fractures were closed and nine were open. Thirty-nine patients used insulin and 45 used oral hypoglycemics or diet for control of their diabetes. Diabetic complications, including nephropathy, hypertension, peripheral vascular disease, and neuropathy were evaluated. The management of diabetes, fracture classification, and presence of diabetic complications were assessed with chi-square, ANOVA, and univariate logistic regression to determine the presence of statistical significance for these factors. Results: Twelve of the 84 patients developed postoperative complications. Ten patients developed infections (eight deep and two superficial). Four of 12 patients with preoperative evidence of peripheral neuropathy developed Charcot arthropathy. Ten of 12 patients who had absent pedal pulses preoperatively developed complications ( p < 0.0001) and 11 of 12 patients with peripheral neuropathy had complications ( p < 0.0001). A trend towards complications was noted with nephropathy (two of five patients) and hypertension (nine of 12 patients). Open fractures, insulin dependence, patient age, and fracture classification had no significant effect on outcome. Conclusions: Most patients with diabetes can undergo open reduction and internal fixation of acute ankle fractures without complications. Patients with absent pedal pulses or peripheral neuropathy are at increased risk for complications.
The Effect of First Ray Shortening in the Development of Metatarsalgia in the Second through Fourth Rays after Metatarsal Osteotomy
Authors: Tóth Kálmán , Huszanyik István , Kellermann Péter , Boda Krisztina , Róde László
Published: February 2007

Background: The aims of this study were to determine the severity of metatarsalgia of the second through fifth rays after shortening of the first ray for correction of hallux valgus deformity and patient satisfaction of the cosmetic results. Methods: Two hundred and forty metatarsal osteotomies (Wilson osteotomy as modified by Lindgren and Turan) were evaluated 4.19 ±1.29 years postoperatively. The procedure involved a slightly oblique subcapital osteotomy of the first metatarsal and fixation with one screw. Results: The average decrease in the hallux valgus angle was 26 ± 5 degrees, the 1–2 intermetatarsal angle was 8.4 ± 4 degrees, and the average shortening of the first metatarsal was 3.8 ± 1.8 mm. Positive correlations were found between metatarsalgia of the second through fourth rays and first ray shortening ( p < 0.001 second ray, p < 0.001 third ray, and p < 0.001 fourth ray); there was no correlation between the fifth ray and first ray shortening. No correlation was found between a decrease in the hallux valgus angle or 1–2 intermetatarsal angle and metatarsalgia in the second through fifth rays. A positive correlation was detected between postoperative foot alignment and decrease in the hallux valgus ( p < 0.001) and a negative correlation between postoperative foot alignment and first ray shortening ( p < 0.01). No correlation was noted between postoperative foot alignment and the 1–2 intermetatarsal angle. Conclusion: Excessive shortening of the first metatarsal should be avoided to decrease the occurrence of postoperative transfer metatarsalgia. We found a greater patient satisfaction with foot alignment in patients who had a greater decrease in the hallux valgus angle and less shortening of the first ray.
The “Kick-off” Position: A New Sign for Early Diagnosis of Complex Regional Pain Syndrome in the Leg
Authors: Panchbhavi Vinod K. , Trevino Saul G. , Castro-Aragon Oscar , Rowell Margaret , Jo Jeannie
Published: February 2007

Background: Complex regional pain syndrome (CRPS) is a clinical entity that develops after a precipitating injury. It involves dysfunction of the sensory, autonomic, and motor systems and frequently is missed on initial presentation. The purpose of this report was to describe a simple clinical sign that can aid in its diagnosis. Methods: A retrospective review was conducted of 39 consecutive patients with CRPS type I or II seen in a foot and ankle clinic between October, 2001, and May, 2005. The diagnosis was based on clinical findings. Results: Twenty-six patients had type I (67%) and 13 patients had type II (33%) CRPS. The most common nerve involved in type II was the superficial peroneal nerve. Each patient, while sitting on the exam table, held the affected extremity with the knee extended against gravity. When the leg was pushed back to a relaxed and suspended position, the patient eventually involuntarily resumed the extended position. This position in which the patients held their legs was termed the “kick-off” position sign. Nine patients were seen at the foot and ankle clinic within 6 weeks of the initial inciting event and had an established “kick-off” position sign within 3 months from the time of injury. The disappearance of this sign correlated with the subsidence of pain. Conclusions: Patients with CRPS have variable clinical presentations. The awareness of this simple observation in the right clinical setting should raise the index of suspicion of CRPS in the differential diagnosis. Early treatment of this syndrome is associated with better outcome.
Effect of Tibiotalar Joint Arthrodesis on Adjacent Tarsal Joint Pressure in a Cadaver Model
Authors: Jung Hong-Geun , Parks Brent G. , Nguyen Augustine , Schon Lew C.
Published: February 2007

Background: Tibiotalar arthrodesis is the most common treatment of end-stage symptomatic ankle arthritis, but concerns exist about late findings of adjacent tarsal joint osteoarthritis. The purpose of this study was to evaluate the changes of pressure in the talonavicular, subtalar, and calcaneocuboid joints before and after rigid tibiotalar joint immobilization and at different levels of tibiopedal dorsiflexion. Methods: Twelve cadaver foot specimens were cyclically loaded on a servohydraulic test frame to 700 N. Joint contact pressure, peak pressure, and contact area in the three tarsal joints were measured before and after tibiotalar joint immobilization with three 6.5-mm screws to simulate ankle arthrodesis. Measurements were obtained at tibiopedal dorsiflexion angles of 0, 10, 20, and 30 degrees in normal ankle joints and at dorsiflexion angles of 0, 10, and 20 degrees in fixed tibiotalar joints. Paired Student's t-tests and one-way ANOVA with repeated measures were used to analyze the data. Results: Joint contact pressures did not show any statistically significant difference for the talonavicular and calcaneocuboid joints in the intact ankle. Contact pressures in the talonavicular and calcaneocuboid joints showed significant differences between 0 and 10 degrees and between 0 and 20 degrees of dorsiflexion ( p < 0.05) in the fused ankle specimens. Comparison of the contact pressure of the talonavicular and the calcaneocuboid joints between the intact and the fused ankle specimens showed a significant difference at 10 and 20 degrees of dorsiflexion ( p < 0.05). Subtalar joint contact pressure in the intact ankle showed a significant difference between 0 and 30 degrees of dorsiflexion ( p < 0.05). Conclusions: These changes in joint pressures and contact area are consistent with findings of transverse tarsal joint arthritis seen in clinical studies. The current findings suggest that a substantial pressure increase in the talonavicular and calcaneocuboid joints at tibiopedal dorsiflexion levels simulating a late stance phase of the gait cycle may be responsible for the secondary tarsal joint degeneration occurring in late ankle arthrodesis.
The Jargon of Pedal Movements
Authors: Greiner Thomas M.
Published: February 2007

Background: All areas of research have their own specialized terms. Typically jargon is used as a short cut among specialists to convey complex ideas with a few brief words or phrases. Several jargons traditionally have been used to describe movements of the foot and ankle. It has been long recognized that these terms have no uniform meanings, which leads to confusion when attempting to synthesize reports from different researchers. Although many researchers are aware of this problem, few seem to be aware of how pervasive it is within the published literature. This report focuses on the depth of variation in uses of the terms inversion and eversion and pronation and supination in describing foot motions. Methods: A survey was sent out via the Internet to three communities: biomechanists, clinical anatomists, and podiatrists. A similar survey was conducted of published articles that appeared during a 10-year period in 16 scientific journals. These surveys provide data on the use and interdependencies of how pronation and supination and inversion and eversion are defined. Results: There are at least 18 different working definitions of inversion and eversion and 20 working definitions of pronation and supination. Several of the definitions were shown to be mutually contradictory. Conclusions: Specialists have failed to describe foot movements in a way that can be unambiguously interpreted. Mutual incomprehensibility of foot movements complicates the interpretive value of any report of foot movements. It is suggested that a new set of terms may help prevent this type of confusion in the future. Clinical Relevance: The lack of unambiguous descriptions in the research literature may mean that clinicians are not always applying treatment options in an appropriate manner. Greater clarity of meaning is required for both basic research and clinical applications.
Understanding and Improving Women’s Health—From Cells to Society
Authors: DeSalvo Karen , Dzau Victor J.
Published: March 2024

This Viewpoint discusses highlights from the National Academy of Medicine 2023 Annual Meeting Scientific Symposium that are representative of key gaps, trends, and opportunities in women’s health.
Transition to Weight-Based High-Flow Nasal Cannula Use Outside of the ICU for Bronchiolitis
Authors: Willer Robert J. , Brady Patrick W. , Tyler Amy N. , Treasure Jennifer D. , Coon Eric R.
Published: March 2024

Importance

Most children’s hospitals have adopted weight-based high-flow nasal cannula (HFNC) bronchiolitis protocols for use outside of the intensive care unit (ICU) setting. Whether these protocols are achieving their goal of reducing bronchiolitis-related ICU admissions remains unknown.

Objective

To measure the association between hospital transition to weight-based non-ICU HFNC use and subsequent ICU admission.

Design, Setting, and Participants

This multicenter retrospective cohort study was conducted with a controlled interrupted time series approach and involved 18 children’s hospitals that contribute data to the Pediatric Health Information Systems database. The cohort included patients aged 0 to 24 months who were hospitalized with a diagnosis of bronchiolitis between January 1, 2010, and December 31, 2021. Data were analyzed from July 2023 to January 2024.

Exposure

Hospital-level transition from ICU-only to weight-based non-ICU protocol for HFNC use. Data for the ICU-only group were obtained from a previously published survey.

Main Outcomes and Measures

Proportion of patients with bronchiolitis admitted to the ICU.

Results

A total of 86 046 patients with bronchiolitis received care from 10 hospitals in the ICU-only group (n = 47 336; 27 850 males [58.8%]; mean [SD] age, 7.6 [6.2] years) and 8 hospitals in the weight-based protocol group (n = 38 710; 22 845 males [59.0%]; mean [SD] age, 7.7 [6.3] years). Mean age and sex were similar for patients between the 2 groups. Hospitals in the ICU-only group vs the weight-based protocol group had higher proportions of Black (26.2% vs 19.8%) and non-Hispanic (81.6% vs 63.8%) patients and patients with governmental insurance (68.1% vs 65.9%). Hospital transition to a weight-based HFNC protocol was associated with a 6.1% (95% CI, 8.7%-3.4%) decrease per year in ICU admission and a 1.5% (95% CI, 2.8%-0.1%) reduction per year in noninvasive positive pressure ventilation use compared with the ICU-only group. No differences in mean length of stay or the proportion of patients who received invasive mechanical ventilation were found between groups.

Conclusions and Relevance

Results of this cohort study of hospitalized patients with bronchiolitis suggest that transition from ICU-only to weight-based non-ICU HFNC protocols is associated with reduced ICU admission rates.
Cholesterol‐regulated cellular stiffness may enhance evasion of NK cell‐mediated cytotoxicity in gastric cancer stem cells
Authors: Zhu Lijuan , Wang Hongjin
Published: March 2024

Gastric cancer has a high rate of recurrence, and as such, immunotherapy strategies are being investigated as a potential therapeutic strategy. Although the involvement of immune checkpoints in immunotherapy is well studied, biomechanical cues, such as target cell stiffness, have not yet been subject to the same level of investigation. Changes in the cholesterol content of the cell membrane directly influence tumor cell stiffness. Here, we investigated the effect of cholesterol on NK cell‐mediated killing of gastric cancer stem‐like cells. We report that surviving tumor cells with stem‐like properties elevated cholesterol metabolism to evade NK cell cytotoxicity. Inhibition of cholesterol metabolism enhances NK cell‐mediated killing of gastric cancer stem‐like cells, highlighting a potential avenue for improving immunotherapy efficacy. This study suggests a possible effect of cancer cell stiffness on immune evasion and offers insights into enhancing immunotherapeutic strategies against tumors.
Toward One‐Way Smoke: Synthesis of Copper‐Based Microclubs with Asymmetric Scattering and Absorption
Authors: Guo Shichen , Boyarsky Michael , Vigil S. Avery , Yu Yifan , Moreno‐Hernandez Ivan A. , Gehm Michael E. , Wiley Benjamin J.
Published: March 2024

The ultimate goal of this work is to create an engineered aerosol that acts as one‐way smoke, i.e. it creates an asymmetric vision environment in which the ability to image objects depends on the viewing direction. To this end, a rapid, one‐pot synthesis of copper‐based microclubs is developed that consists of a Cu2O octahedron attached to a Cu2O@Cu shaft. Millions of synthesized particles are analyzed in minutes with a FlowCam to provide a robust statistical analysis of their geometry, and rapidly elucidate the roles of the reaction constituents on the particle shape and yield. The combination of asymmetry in both shape and composition introduces a 30% difference in scattering of light propagating parallel to the microclub axis from opposing directions. This work represents a first step toward the creation of an asymmetric imaging environment with an aerosol consisting of acoustically aligned microclubs.
Recent Design Strategies for M‐N‐C Single‐Atom Catalysts in Oxygen Reduction: An Entropy Increase Perspective
Authors: Yan Wei , Chen Wenmiao , Chen Yanli
Published: March 2024

Recently, a diverse array of novel metal‐nitrogen‐carbon (M‐N‐C) single‐atom catalysts (SACs) have rapidly evolve, particularly in the realm of oxygen reduction reaction (ORR). Despite the plethora of proposed design and improvement strategies for SACs, a comprehensive review systematically compiling the components in M‐N‐C from a unified perspective is notably absent. For the first time, a thorough examination of each component in M‐N‐C is conducted, focusing on the perspective of entropy increase in the active sites of SACs. For the single M‐N4 sites and the whole M‐N‐C system, an increase in entropy implies an elevated degree of disorder and chaos. Broadly, the entropy‐increasing modification of M (single mental sites) and guest groups entails an augmentation of chaos, with the most effective co‐catalytic synergy achieved by establishing multiple active sites through a “cocktail effect”. Concerning N (nitrogen and other heteroatoms) and C (carbon supports), the entropy increase modification induces heightened disorder, with symmetry breaking more likely to drive M‐N4 toward adsorbing oxygen molecules to attain an equilibrium symmetric structure. All these innovative design strategies have led to a remarkable improvement in the ORR activity and stability and offer a guiding criterion for the future preparation of SACs.
Precursor Symmetry Triggered Modulation of Fluorescence Quantum Yield in Graphene Quantum Dots
Authors: Chen Liangfeng , Yang Siwei , Li Yongqiang , Liu Zheng , Wang Hang , Zhang Yuqing , Qi Kai , Wang Gang , He Peng , Ding Guqiao
Published: March 2024

Although various effective machine‐learning attempts have been made to investigate the photoluminescence properties of graphene quantum dots (GQDs) or carbon dots, the physical correlation behind their mathematical models has not been reasonably elucidated. In this work, the correlation mechanism between the precursor structure and quantum yield of GQDs prepared by a “bottom‐up” method is sufficiently studied. Three decisive factors affecting the quantum yield of GQDs during the two‐component reaction system preparation are revealed, namely structure factor (F1), temperature factor (F2), and concentration factor (F3). The symmetry of precursors in the formation of sp2–sp3 hybrid carbon nanostructures is considered the key factor in the modulation of fluorescence quantum yield in GQDs. Notably, in contrast to previous work, it is first demonstrated that the normal modes of molecular vibration are the core mechanism by which the structural properties of the precursors act on the fluorescence quantum yield of GQDs. The conclusion further proved conducive in obtaining GQDs with a higher absolute quantum yield up to 83.33%.
Centimeter‐Size Single Crystal of a Polar Dion–Jacobson Double Perovskite with Large Mobility‐Lifetime Product toward Effective X‐Ray Detection
Authors: Guo Wuqian , Xu Haojie , Fan Qingshun , Zhu Pengfei , Ma Yu , Liu Yi , Zeng Xi , Luo Junhua , Sun Zhihua
Published: March 2024

Dion–Jacobson (DJ) double perovskites have emerged as environmentally friendly candidates for X‐ray detection, owing to their prominent optoelectronic performance and highlighted structural rigidity. Despite considerable efforts, the exploration of polar DJ‐type double perovskites for self‐powered X‐ray detection remains scarce. Herein, by introducing a diamine spacer to increase the structural rigidity, the study has successfully designed a new polar 2D DJ‐type double perovskite of (HIA)2AgBiBr8 (1, HIA = histamine), and centimeter‐size crystals are successfully obtained for effective X‐ray detection. Structurally, 1 features the quantum‐confined motif comprised of the directionally arranged inorganic perovskite sheets and alternating organic spacing cations, which endows a large mobility‐lifetime (µτ) product up to 1.23 × 10−3 cm2 V−1 on the par with typical X‐ray sensing candidates (MAPbI3 wafers, µτ = 2 × 10−3 cm2 V−1). This attribute gives rise to a high sensitivity of 118 µCGyair−1 cm−2 to X‐ray illumination. Moreover, based on its polar structure, bulk photovoltaic effect with the photovoltage of ≈0.45 V is obtained in 1, which affords the driving source toward the self‐powered X‐ray photodetection. This work highlights the potential of DJ‐type double perovskites in high‐energy ray detection and opens avenues for exploring new functionalities of DJ double perovskites as smart photoelectric candidates.
Ni active sites isolated by antimony toward enhanced propyne semi‐hydrogenation
Authors: Xi Jiahang , Yan Kelin , Zhu Ningchao , Ge Xiaohu , Yuwen Qiang , Chen Mingming , Jiang Hao , Cao Yueqiang , Zhou Xinggui , Duan Xuezhi
Published: March 2024

Regulating Ni active sites toward the formation of target product is of great importance for designing high‐performance cost‐effective catalysts for catalytic semi‐hydrogenations but remains challenging. Herein, we report the fabrication of NiSb intermetallic catalyst via structural transformation from a layered double hydroxides precursor for boosting propyne semi‐hydrogenation. Systematic characterizations, including x‐ray diffraction, atomic‐resolution electron microscopy, and x‐ray absorption spectroscopy, provide evidence for the formation of P63/mmc NiSb intermetallic phase in the synthesized NiSb catalyst. The host Ni active sites are demonstrated to be isolated by the high‐electronegativity p‐block guest Sb sites, which deliver remarkably high selectivity to target propene, that is, up to propene selectivity of 96% at nearly full propyne conversion. Temperature‐programmed surface reaction and temperature‐programmed desorption measurements combined with theoretical calculations unravel that the excellent selectivity originates from kinetically more favorable desorption of propene than its hydrogenation to propane on the regulated Ni active sites.
Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic‐Inorganic Crystal by In Situ X‐Ray Diffraction
Authors: Morris Joshua J. , Bowen Chris R. , Coulson Ben A. , Eaton Mark , Raithby Paul R. , Saunders Lucy K. , Skelton Jonathan M. , Wang Qingping , Warren Mark R. , Zhang Yan , Hatcher Lauren E.
Published: March 2024

The switching behavior of the novel hybrid material (FA)Na[Fe(CN)5(NO)].H2O (1) in response to temperature (T), light irradiation and electric field (E) is studied using in situ X‐ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation. XRD shows that the FA+ are disordered at room‐temperature, but stepwise cooling from 273–100 K induces gradual ordering, while cooling under an applied field (E=+40 kVcm−1) induces a sudden phase change at 140 K. Structural‐dynamics calculations suggest the field pushes the system into a region of the structural potential‐energy surface that is otherwise inaccessible, demonstrating that application of T and E offers an effective route to manipulating the crystal chemistry of these materials. Photocrystallography also reveals photoinduced linkage isomerism, which coexists with but is not correlated to other switching behaviors. These experiments highlight a new approach to in situ studies of hybrid materials, providing insight into the structure–property relationships that underpin their functionality.
Radicalizing CO by Mononuclear Palladium(I)
Authors: Bruckhoff Tim , Ballmann Joachim , Gade Lutz H.
Published: March 2024

A mononuclear, T‐shaped palladium(I) d9 metalloradical (3), stabilized by a bulky carbazole‐based PNP‐ligand, was obtained by reduction of palladium chloride or thermal Pd−C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structurally characterized by X‐ray diffraction. Delocalization of the unpaired electron to the carbonyl carbon was detected by EPR spectroscopy and theoretically modeled by DFT and ab initio methods. The partially reduced and radicalized CO slowly reacts with di(tert‐butyl) disulfide under homolytic S−S cleavage and C−S bond formation to give the corresponding metallathioester.
Mode‐Selective Spin–Phonon Coupling in van der Waals Antiferromagnets
Authors: Rao Rahul , Selhorst Ryan , Siebenaller Ryan , Giordano Andrea N. , Conner Benjamin S. , Rowe Emmanuel , Susner Michael A.
Published: March 2024

2D magnetic materials offer the opportunity to study and manipulate emergent collective excitations. Among these, spin–phonon coupling is one of the most important interactions correlating charge, spin and lattice vibrations. Understanding and controlling this coupling is important for spintronics applications, control of magnons and phonon by THz radiation, and for strain‐driven magnetoelastic applications. Here, a resonant mode‐selective spin–phonon coupling in several magnetic 2D metal thiophosphates (NiPS3, FePS3, CoPS3 and MnPS3) through multi‐excitation and temperature‐dependent Raman scattering measurements is uncovered. The phonon mode, which is a Raman‐active out‐of‐plane vibrational mode (∼250 cm−1 or 7.5 THz), exhibits an asymmetric Fano lineshape where its asymmetry is proportional to the spin–phonon coupling. The measurements reveal the coupling to be the highest in NiPS3, followed by FePS3 and CoPS3, and least in MnPS3. These differences are attributed to the metal–sulfur interatomic distances, which are the lowest in NiPS3, followed by CoPS3, FePS3 and MnPS3. Finally, the spin–phonon coupling is also observed in exfoliated materials, with a slight reduction between 20 and 30% in the thinnest flakes compared to the bulk crystals.
Backward stochastic Volterra integral equations with time delayed generators
Authors: Coulibaly Harouna , Aman Auguste
Published: March 2024

In this paper, we study backward stochastic Volterra integral equations of type‐I with time delayed generators. We derive an existence and uniqueness result under a small time horizon or a small Lipschitz constant. We provide with two example that this condition is necessary. However, this equation has a unique solution for arbitrary time horizon and Lipschitz constant. Finally, with additive assumptions, we derive a path continuity property.
Highly chromophoric fluorescent‐labeled methionyl‐initiator tRNAs applicable in living cells
Authors: Kim Jung Min , Jung Jinho
Published: March 2024

Fluorescent initiator tRNAs (tRNAi) play a crucial role in studying protein synthesis, yet generating highly fluorescent tRNAi complexes remains challenging. We present an optimized strategy to effectively generate highly fluorescent initiator‐tRNA complexes in living cells. Our strategy allows the generation of Fluo‐Met‐tRNAiMet complexes. These complexes can have highly chromogenic N‐terminal labeling. For generating such complexes, we use either purified fluorescent methionine (PFM) or non‐purified fluorescently labeled methionine (NPFM). Furthermore, PFM promotes the active generation of endogenous tRNAi in cells, leading to highly efficient Fluo‐Met‐tRNAiMet complexes. Finally, PFM‐tRNAiMet complexes also facilitate the visualization of native fluorescently labeled Tat binding to beads. This demonstrates the potential of our approach to advance precision protein engineering and biotechnology applications.
Itaconic acid production by co‐feeding of Ustilago maydis: A combined approach of experimental data, design of experiments, and metabolic modeling
Authors: Ziegler Anita L. , Ullmann Lena , Boßmann Manuel , Stein Karla L. , Liebal Ulf W. , Mitsos Alexander , Blank Lars M.
Published: March 2024

Itaconic acid is a platform chemical with a range of applications in polymer synthesis and is also discussed for biofuel production. While produced in industry from glucose or sucrose, co‐feeding of glucose and acetate was recently discussed to increase itaconic acid production by the smut fungus Ustilago maydis. In this study, we investigate the optimal co‐feeding conditions by interlocking experimental and computational methods. Flux balance analysis indicates that acetate improves the itaconic acid yield up to a share of 40% acetate on a carbon molar basis. A design of experiment results in the maximum yield of 0.14 itaconic acid per carbon source from 100  glucose and 12  acetate. The yield is improved by around 22% when compared to feeding of glucose as sole carbon source. To further improve the yield, gene deletion targets are discussed that were identified using the metabolic optimization tool OptKnock. The study contributes ideas to reduce land use for biotechnology by incorporating acetate as co‐substrate, a C2‐carbon source that is potentially derived from carbon dioxide.
Theoretical analysis on the formation and nitric oxide release of N‐heterocyclic carbene nitric oxide radicals
Authors: Park Junbeom , Song Hayoung , Lee Yong Ho , Lee Eunsung
Published: March 2024

The theoretical study on the fixation and release of nitric oxide (NO) by N‐heterocyclic carbenes (NHCs) is explored by utilizing a multivariate linear regression approach. We utilized data‐driven tools to establish correlations between molecular descriptors of NHC and reaction outputs of the formation and NO release of NHC nitric oxide radicals (NHCNOs). A key electronic parameter, the singlet‐triplet energy gap (ΔEST), plays a pivotal role in the thermodynamics of NHCNO formation (ΔGf) and NO release (ΔGr). The activation energy models highlight HOMO energy level (EHOMO), C–N bond length (dC–N), and NBO charge on N atom (qNBON) as crucial factors for the formation of NHCNO (ΔG‡f), while the activation energy for the NO release (ΔG‡r) significantly correlates with free energy difference (ΔGr), resulting a strong ΔEST dependency. This study provides valuable insights into the thermodynamics and kinetics of NHCNO processes, offering predictive capabilities to design NHCs tailored for NO release.
Cancer patients with clonal hematopoiesis die from primary malignancy or comorbidities despite higher rates of transformation to myeloid neoplasms
Authors: Chien Kelly S. , Ong Faustine , Kim Kunhwa , Li Ziyi , Kanagal‐Shamanna Rashmi , DiNardo Courtney D. , Takahashi Koichi , Montalban‐Bravo Guillermo , Hammond Danielle , Sasaki Koji , Pierce Sherry A. , Kantarjian Hagop M. , Garcia‐Manero Guillermo
Published: March 2024

Background

The occurrence of somatic mutations in patients with no evidence of hematological disorders is called clonal hematopoiesis (CH). CH, whose subtypes include CH of indeterminate potential and clonal cytopenia of undetermined significance, has been associated with both hematologic cancers and systemic comorbidities. However, CH's effect on patients, especially those with concomitant malignancies, is not fully understood.

Methods

We performed a retrospective evaluation of all patients with CH at a tertiary cancer center. Patient characteristics, mutational data, and outcomes were collected and analyzed.

Results

Of 78 individuals included, 59 (76%) had a history of cancer and 60 (77%) had moderate to severe comorbidity burdens. DNMT3A, TET2, TP53, and ASXL1 were the most common mutations. For the entire cohort, the 2‐year overall survival rate was 79% (95% CI: 70, 90), while the median survival was not reached. Of 20 observed deaths, most were related to primary malignancies (n = 7, 35%), comorbidities (n = 4, 20%), or myeloid neoplasms (n = 4, 20%). Twelve patients (15%) experienced transformation to a myeloid neoplasm. According to the clonal hematopoiesis risk score, the 3‐year transformation rate was 0% in low‐risk, 15% in intermediate‐risk (p = 0.098), and 28% in high‐risk (p = 0.05) patients. By multivariate analysis, transformation was associated with variant allele frequency ≥0.2 and hemoglobin <10 g/dL.

Conclusions

In a population including mostly cancer patients, CH was associated with comorbidities and myeloid transformation in patients with higher mutational burdens and anemia. Nevertheless, such patients were less likely to die of their myeloid neoplasm than of primary malignancy or comorbidities.
Benzimidazole and Benzoxazole Derivatives Against Alzheimer's Disease
Authors: Faydalı Nagihan , Arpacı Özlem Temiz
Published: March 2024

Benzimidazole and benzoxazole derivatives are included in the category of medical drugs in a wide range of areas such as anticancer, anticoagulant, antihypertensive, anti‐ inflammatory, antimicrobial, antiparasitic, antiviral, antioxidant, immunomodulators, proton pump inhibitors, hormone modulators, etc. Many researchers have focused on synthesizing more effective benzimidazole and benzoxazole derivatives for screening various biological activities. In addition, there are benzimidazole and benzoxazole rings as bioisosteres of aromatic rings found in drugs used in the treatment of Alzheimer's disease. Because of the diverse activity of the benzimidazole and benzoxazole rings and bioisosteres marketed as drugs for Alzheimer Diseases, designed compounds containing these rings are likely to be effective against Alzheimer's disease. In this study, the effectiveness of compounds containing benzimidazole and benzoxazole rings against Alzheimer's disease will be examined.
In vitro Evaluation of Skin Related Enzyme Inhibitory Effect and Emulgel Formulation Development Studies of Onobrychis Argyrea subsp. Argyrea with Phytochemical Analysis
Authors: Şentürk Tuğba Buse , Barak Timur Hakan , Çağlar Emre Şefik , Nath Ebru Özdemir , Özdemir Zafer Ömer
Published: March 2024

Species of Onobrychis have been used to treat skin disorders such as wounds and cuts in folk medicine and Onobrychis argyrea subsp. argyrea (OA) commonly known as ‘silvery sainfoin’, is a member of this genus. In this study, it was aimed to investigate the skin‐related biological activities and phytochemical characterization of OA. Moreover, an emulgel formulation was developed from the main methanolic extract of the plant (OAM). Initially, to identifiy of the active fractions, aerial parts of the plant material was extracted with methanol and fractionated by n‐hexane, chloroform, ethyl acetate and n‐butanol, respectively. Antioxidant activity was determined by CUPRAC, TOAC, FRAP and DPPH assays. Thereafter, the inhibition potential of OAM, novel formulation and all fractions was measured against elastase, collagenase, tyrosinase and hyaluronidase enzymes. OAM was analyzed and characterized by LC/MS‐MS. The major bioactive flavonoids which are rutin and isoquercetin were measured and compared as qualitative and quantitative via high performance thin layer chromatography (HPTLC) analysis in OAM and fractions. The results showed that extracts of OA can be a potential cosmeceutical agent for skin related problems.
Revolutionizing Infection Control: Harnessing MXene‐Based Nanostructures for Versatile Antimicrobial Strategies and Healthcare Advancements
Authors: Habeeb Naser Israa , Ali Naeem Youssef , Ali Eyhab , Yarab Hamed Amina , Farhan Muften Nafaa , Turky Maan Fadhil , Hussein Mohammed Israa , Mohammad Ali Khalil Noor Alhuda , Ahmad Irfan , Abed Jawad Mohammed , Elawady Ahmed
Published: March 2024

The escalating global health challenge posed by infections prompts the exploration of innovative solutions utilizing MXene‐based nanostructures. Societally, the need for effective antimicrobial strategies is crucial for public health, while scientifically, MXenes present promising properties for therapeutic applications, necessitating scalable production and comprehensive characterization techniques. Here we review the versatile physicochemical properties of MXene materials for combatting microbial threats and their various synthesis methods, including etching and top‐down or bottom‐up techniques. Crucial characterization techniques such as XRD, Raman spectroscopy, SEM/TEM, FTIR, XPS, and BET analysis provide insightful structural and functional attributes. The review highlights MXenes’ diverse antimicrobial mechanisms, spanning membrane disruption and oxidative stress induction, demonstrating efficacy against bacterial, viral, and fungal infections. Despite translational hurdles, MXene‐based nanostructures offer broad‐spectrum antimicrobial potential, with applications in drug delivery and diagnostics, presenting a promising path for advancing infection control in global healthcare.
Mother–daughter technique for kinked catheter retrieval from radial artery
Authors: Panchal Hemang B. , Patel Nirav , Bhogal Sukhdeep , De La Cruz Quezada Kristal
Published: March 2024

Catheter kinking is not an uncommon scenario during cardiac catheterization via transradial access in patients with tortuous vascular anatomy. Several noninvasive and invasive methods have been described to unkink and retrieve the kinked catheter out of the vessel. We present a novel mother–daughter technique to retrieve a kinked radial artery catheter.