bluuebunny/crossref_metadata_2025 huggingface dataset:
Spectrum of Seasonal Allergic Rhinitis Symptom Relief with Topical Corticoid and Oral Antihistamine Given Singly or in Combination
Authors: Brooks Carter D. , Francom Steven F. , Peel Bruce G. , Chene Brenda L. , Klott Karen A.
Published: September 2007

Sixty ragweed-sensitive volunteers participated in a 2-week study that compared symptom profiles during treatment with antihistamine (loratadine, LOR) alone, topical corticoid (beclomethasone, BEC) alone, or the two drugs combined. For 5 days commencing shortly after the beginning of the ragweed bloom, patients took no treatment while we collected baseline data. They were then randomized to one of the three treatments, receiving that treatment for the balance of the 2-week study term. Twice each day they recorded the severity of congestion, eye symptoms, running and blowing, itching, and sneezing. At the end of the study they provided an estimate of overall symptom relief, which favored combined treatment (vs LOR P = 0.001, vs BEC P = 0.042). To gain an estimate of disease severity and treatment effectiveness over time, and to smooth out day-to-day variation, we divided symptom diary reports into three segments (days 2–4, 5–7, and 8–10) for analysis. Combined treatment controlled symptoms better than antihistamine alone in nearly all study segments. Corticoid alone or combined with antihistamine provided similar control of congestion, running and blowing, and eye complaints. Combination therapy controlled itching and sneezing better, especially through the study segments 1 and 2. Patient preference for combined treatment seems to relate to control of itching and sneezing and rapid onset of effect.
Immunohistochemical Analysis of Mononuclear Inflammatory Cells in Nasal and Sinus Epithelium in Children with Sinusitis
Authors: Pena Maria , Brodsky Linda , Gorfien Janet , Noble Bernice
Published: September 2007

The etiology and pathophysiology of both recurrent acute and chronic sinusitis in children are not well understood. To investigate this problem, the nature and magnitude of the local cellular inflammatory response was evaluated in the sinus mucosa of 34 children (25 with chronic sinusitis and 9 with recurrent acute sinusitis), of which 27 are atopic and 7 are nonatopic. In addition, sinus mucosa from three patients who underwent sinus surgery for noninfectious sinus disease (two with antral choanal polyp and one with facial pain syndrome) was studied for comparison and “controls. “ Immunohistochemical methods were used to identify phenotypically distinct mononuclear cells subpopulations (B cells, T cells, macrophages, and MHC class II antigen presenting cells) in the epithelium, stroma, and periglandular compartments of the uncinate and ethmoid mucosal tissue layers. Eosinophils were assessed in the same sinus mucosal tissue compartments and in nasal secretions. For all patients, most of the inflammatory cells were found in the stroma. MHC class II positive cells and T cells were found in the epithelium of greater than 50%, and in the stroma of almost 100% of either the uncinate or ethmoid mucosa. Of interest, the local accumulation of tissue eosinophils and/or their presence in nasal smears was not closely linked to the presence of atopy. In three patients with noninfectious sinusitis, the majority of inflammatory cells had also accumulated in the stroma; the mononuclear cell subset composition in those controls was indistinguishable from the sinusitis population. No difference in the number and distribution of any inflammatory cell subset was noted with respect to clinical classification, atopy or immunocompetency profile in our patient population. These observations indicate that the mucosal surfaces studied were likely to have been immunocompetent. Taken together, the uniformly modest local inflammation and the similarity of cell subpopulations in patients with different clinical profiles suggest that local inflammatory mechanisms may not account for clinical differences in the pathophysiology of sinusitis.
A Head and Tube Stabilizing Apparatus for Acoustic Rhinometry Measurements
Authors: Roth Yehudah , Furlott Henry , Coost Cathy , Roithmann Renato , Cole Phillip , Chapnik Jerry S. , Zamel Noe
Published: September 2007

A new apparatus consisting of a chin rest and forehead support system and an adjustable acoustic tube holder is described. This device provides patient comfort, technical convenience and precise positioning that contribute to reliable measurement. Moderate pressure between forehead and supporting bar incorporated into the apparatus did not induce significant alterations in results.
The Identification of the Potential Limitations of Acoustic Rhinometery Using Computer-Generated, Three-Dimensional Reconstructions of Simple Models
Authors: Tomkinson A. , Eccles R.
Published: September 2007

The internal surface of the nasal cavity is geometrically complicated and does not lend itself readily to direct measurement. Simple geometric shapes were used as a model for changes in the nasal cavity. Following the introduction of specific changes to a particular system, the effect of these changes on the acoustic evaluation of the space was studied. Cylinders were chosen, as the wave path could be assumed to be perpendicular to the model surface. The acoustic rhinometer's accuracy was assessed in the presence of small and large variations in cross sectional area, in the presence of a series of consecutive area changes, and a gradual change in diameter. The effect of the introduction of acoustic leak was also modelled. The acoustic data acquired from these models was used to reconstruct the model in three dimensions. These reconstructions were compared to the original model. The acoustic rhinometer was found to resolve with reasonable accuracy the dimensions of small spaces; however, if regions of sudden large area changes were present in the space, the data beyond these regions was highly unreliable. Furthermore, the presence of acoustic leak in a system had a similar effect. Unless precautions are taken in the set-up and operation of the acoustic rhinometer, the potential for misinterpretation of data and the introduction of bias is very high.
Intranasal Endoscopic Surgery with Silicone Intubation for Lacrimal Obstruction
Authors: Önerci Metin , Orhan Mehmet , Erdener Uğur
Published: September 2007

Endoscopic intranasal dacryocystorhinostomy (DCR) with silicone intubation has been evaluated as a primary treatment of lacrimal obstruction in 30 patients and for revision of conventional DCRs in 4 patients. Lacrimal obstruction was completely relieved in 28 (93.3%) of 30 primary procedure patients, and in three of four previously operated patients after a mean follow-up of 18 months. No intraoperative complications were observed. The average period of time of silicone tube intubation was 2 months. Intranasal endoscopic DCR with silicone intubation is an effective method in treatment of nasolacrimal duct obstructions and should also be considered in patients with recurrent epiphora after external DCR.
Active Transport Dacryocystography in Evaluating Lacrimal Drainage System after Rhinoplasty
Authors: Ünlü H. Halis , Çaylan Refik , Kutlu Necmettin , Imamoğlu Mehmet , Ünal Mustafa , Yücetürk Ali Vefa
Published: September 2007

In order to evaluate the effects of lateral osteotomies performed during rhinoplastic surgery on the lacrimal drainage system, a new technique for imaging the lacrimal passages, Active Transport Dacryocystography, was applied in a total of 16 patients. In all cases, free passage of contrast media from the punctum to the inferior meatus was observed. We did not record any pathologic alteration such as mucosal edema or discontinuity of the bony structure that would have resulted in nasolacrimal obstruction.
FESS with and without the Availability of CT Imaging
Authors: Lopatin Andrey S. , Piskunov Gennady Z.
Published: September 2007

A series of 322 endonasal endoscopic interventions in 200 patients was reviewed. The patients were divided into two groups: I - consisting of the patients undergoing surgery without preoperative CT of paranasal sinuses; II - where CT was available and was performed before surgery. In both groups no major complications occurred, and the incidence of minor complications was similar. Adherence to anatomical landmarks was of paramount importance and reduced the incidence of complications in both groups. Experience in endonasal surgery, control of bleeding by meticulous technique, local anesthesia, and proper patient selection allowed the surgeon to avoid injury during FESS.
An Evaluation of Active Anterior and Posterior Rhinomanometry in British Adults
Authors: Canbay Ercan I. , Bhatia Suren N.
Published: September 2007

In this study, active Anterior Rhinomanometry (ARM) and Posterior Rhinomanometry (PRM) were performed sequentially by 56 normal British Caucasian adults using an on-line Mercury Electronics NR6D Rhinomanometer. Xylometazoline nasal spray was used as a nasal decongestant before the test. In addition, repeated measurements were made on a randomly selected 13 subjects to evaluate the error of the methods. The mean total nasal airway resistance by the anterior method was found to be 0.182 Pa/cm3/s at a reference pressure of 150 Pascals, and by the posterior method 0.166 Pa/cm3/s at a reference pressure of 75 Pascals. These mean values are similar to those reported by other authors for Caucasians. The errors of the methods were found to be smaller than previously reported (Coefficient of variation, ARM = 6.9%; PRM = 7.7%). The total nasal airway resistance was higher during expiration than inspiration, and higher in women than in men. The ARM values were on an average 9% higher than those of the PRM, and the association between the two values was found to be moderate (r = 0.48). The higher ARM mean values could be attributed to inappropriateness of the conventional Ohm's law used in their calculation. For a number of reasons, PRM is considered to be more suitable than ARM for measuring nasal resistance.
Pyogenic Granuloma—An Uncommon Complication of Nasal Packing
Authors: Sheen Tzung-Shiahn , Ko Jenq-Yuh , Hsu Yung-Hsiang
Published: September 2007

Nasal packing is a very common procedure in the otolaryngologic service for nasal bleeding and postoperative hemostasis. However, a pyogenic granuloma complicated from nasal packing has not been reported in the literature. A 50-year-old man underwent nasal packing by use of vaseline gauze due to nasal bleeding. Two weeks later, a dark brown nasal tumor was found in his nasal cavity. He underwent partial turbinectomy for removal of the tumor. The pathology demonstrated a pyogenic granuloma. It is the first case of a confirmed pyogenic granuloma complicated from nasal packing in the literature. To prevent complications and decrease the discomfort, we strongly recommend the use of inflatable balloons or nontraumatic materials for nasal packing.
Effects of Anti-Allergic Drugs on Substance P (SP) and Vasoactive Intestinal Peptide (VIP) in Nasal Secretions
Authors: Shinoda Mitsunori , Watanabe Noritake , Suko Takeshi , Mogi Goro , Takeyama Masaharu
Published: September 2007

To clarify the effects of anti-allergic drugs on substance P (SP) and vasoactive intestinal peptide (VIP) levels in nasal secretions, we employed competitive enzyme-linked immunoassays to measure concentrations of those neuropeptides in nasal secretions from 40 patients with house dust nasal allergy before and after administration of azelastine and oxatomide. One mg of azelastine and 30 mg of oxatomide were administrated twice a day for 4 weeks. Mean values of SP concentrations and ratios of SP to total protein of the nasal allergy group were significantly higher than those of the control group (p < 0.002). The VIP/total protein ratio of the allergy group was also significantly higher than that of the control group, although the VIP concentration alone was not. Mean levels of SP and VIP from patients with severe symptoms were significantly higher than those of the control group (p < 0.05), although those values were not significantly different between patients with moderate symptoms and control subjects. Azelastine and oxatomide effectively reduced SP levels in nasal secretions (p < 0.005), but they did not significantly decrease VIP levels. The reduction of SP levels was significant in patients with excellent responses to those drugs (p < 0.005), but not in patients with poor responses. These findings suggest that SP and VIP levels in nasal secretions may reflect the clinical state of nasal allergy and be one of the better parameters available for evaluating the clinical efficacy of anti-allergic drugs against nasal allergy.
The Anatomic Relevance of the Haller Cell in Sinusitis
Authors: Stackpole Sarah A. , Edelstein David R.
Published: September 2007

In current theories of sinusitis, obstruction at the ostiomeatal complex leads to localized inflammation and infection. Haller cells, an extension of ethmoid pneumatization along the maxillary antrum roof, have also been suggested as a causative factor in sinusitis because of their ability to cause narrowing of the infundibulum. Coronal CT scans were reviewed in 154 patients to evaluate the role of Haller cells in sinusitis. Haller cells were present in 34% of patients. The cells were graded as small, medium, or large, and correlated with radiologic evidence of sinusitis (e.g., mucosal thickening or opacification). A statistically significant increase in maxillary sinus mucosal disease was noted in patients with medium or large Haller cells (45.8%) versus those with small cells (28.9%, p < 0.05). Thus obstructive medium and large Haller cells may be an etiologic factor in sinusitis.
Evaluation of Prognostic Factors in Endoscopic Sinus Surgery
Authors: Marks Steven C. , Shamsa Falah
Published: September 2007

A retrospective analysis of 115 consecutive patients who underwent endoscopic sinus surgery for chronic sinusitis was conducted to evaluate the effect on outcome of variables including previous sinus surgery, allergy, asthma, and computed tomography stage of disease. Outcome was assessed in each patient by a survey in which the patient rated the benefit of surgery in terms of percent improvement in different symptoms compared with symptoms before surgery. Outcome was also assessed by the need for revision surgery and the presence of endoscopic criteria for failure. The results indicate that allergy and previous sinus surgery are associated with lower individual symptom scores, but no variable was associated with overall symptomatic failure. Previous sinus surgery was strongly associated with the need for subsequent revision surgery. The computed tomography stage was strongly associated with endoscopic evidence of failure. In conclusion, both history of previous sinus surgery and computed tomography stage of disease are correlated to poor outcomes after endoscopic sinus surgery.
Exclusive Breastfeeding Duration and Risk of Childhood Cancers
Authors: Søegaard Signe Holst , Andersen Mie Mølgaard , Rostgaard Klaus , Davidsson Olafur Birgir , Olsen Sjurdur Frodi , Schmiegelow Kjeld , Hjalgrim Henrik
Published: March 2024

Importance

Breastfeeding has been suggested to protect against childhood cancers, particularly acute lymphoblastic leukemia (ALL). However, the evidence stems from case-control studies alone.

Objective

To investigate whether longer duration of exclusive breastfeeding is associated with decreased risk of childhood ALL and other childhood cancers.

Design, Setting, and Participants

This population-based cohort study used administrative data on exclusive breastfeeding duration from the Danish National Child Health Register. All children born in Denmark between January 2005 and December 2018 with available information on duration of exclusive breastfeeding were included. Children were followed up from age 1 year until childhood cancer diagnosis, loss to follow-up or emigration, death, age 15 years, or December 31, 2020. Data were analyzed from March to October 2023.

Exposure

Duration of exclusive breastfeeding in infancy.

Main Outcomes and Measures

Associations between duration of exclusive breastfeeding and risk of childhood cancer overall and by subtypes were estimated as adjusted hazard ratios (AHRs) with 95% CIs using stratified Cox proportional hazards regression models.

Results

A total of 309 473 children were included (51.3% boys). During 1 679 635 person-years of follow-up, 332 children (0.1%) were diagnosed with cancer at ages 1 to 14 years (mean [SD] age at diagnosis, 4.24 [2.67] years; 194 boys [58.4%]). Of these, 124 (37.3%) were diagnosed with hematologic cancers (81 [65.3%] were ALL, 74 [91.4%] of which were B-cell precursor [BCP] ALL), 44 (13.3%) with central nervous system tumors, 80 (24.1%) with solid tumors, and 84 (25.3%) with other and unspecified malignant neoplasms. Compared with exclusive breastfeeding duration of less than 3 months, exclusive breastfeeding for 3 months or longer was associated with a decreased risk of hematologic cancers (AHR, 0.66; 95% CI, 0.46-0.95), which was largely attributable to decreased risk of BCP-ALL (AHR, 0.62; 95% CI, 0.39-0.99), but not with risk of central nervous system tumors (AHR, 0.96; 95% CI, 0.51-1.88) or solid tumors (AHR, 0.87; 95% CI, 0.55-1.41).

Conclusions and Relevance

In this cohort study, longer duration of exclusive breastfeeding was associated with reduced risk of childhood BCP-ALL, corroborating results of previous case-control investigations in this field. To inform future preemptive interventions, continued research should focus on the potential biologic mechanisms underlying the observed association.
A 3D‐Printed Printhead: Custom Inkjet Dispenser for Medium Viscosity Fluids
Authors: Raposo Pinto Rui Miguel , Faraji Mohammadmahdi , Vinayakumar Kadayra Basavarajappa
Published: March 2024

Inkjet is a versatile non‐contact printing technique that uses droplets of ink jetted from nozzles to print on a variety of substrates. Although some modern piezoelectric printheads support high viscosity fluids (>10 cP), they are currently expensive and may not be suited for many benchtop experiments in research environment. Here, the design, fabrication by 3D‐printing (no cleanroom processes or silicon micromachining are involved) and testing of a multi‐purpose single‐nozzle piezoelectric dispenser/printhead for medium‐viscosity fluids (10–60 cP) is reported. Custom control electronics are developed to drive the printhead. The design features a 200 μm diameter nozzle, suitable for nL drop generation with solutions containing nm sized particles, thus allowing the deposition of μm thick layers of functional inks in a single printing pass. The inkjet dispenser is first tested with glycerol solutions, resulting in drops of 1.9–3.6 nL with typical drop velocity of 0.5–1.3 m s−1. The developed piezoelectric dispensing system is then demonstrated in the printing of a two‐layer capacitive sensor, using silver nanoparticle ink (conductive ink) and a transparent encapsulant ink (dielectric ink). The reported piezoelectric dispenser design can be optimized for many research purposes, allowing the dispensing of functional chemicals, materials, and biomolecules.
Lattice Oxygen Redox Mechanisms in the Alkaline Oxygen Evolution Reaction
Authors: Ren Xiangrong , Zhai Yiyue , Yang Na , Wang Bolun , Liu Shengzhong (Frank)
Published: March 2024

Understanding of fundamental mechanism and kinetics of the oxygen evolution reaction (OER) is pivotal for designing efficient OER electrocatalysts owing to its key role in electrochemical energy conversion devices. In the past few years, the lattice oxygen oxidation mechanism (LOM) arising from the anodic redox chemistry has attracted significant attention as it involves a direct O─O coupling and thus bypasses thermodynamic limitations in the traditional adsorbate evolution mechanism (AEM). Transition metal‐based oxyhydroxides are generally acknowledged as the real catalytic phase in alkaline media. In particular, their low‐dimensional layered structures offer sufficient structural flexibility to trigger the LOM. Herein, a comprehensive overview is provided for recent advances in anion redox from LOM‐based electrocatalysts. Based on analyses of electronic structure of electrocatalysts and LOM, a strategy is proposed to activate LOM. Possible identification techniques for corroboration of the oxygen redox are also reviewed. In addition, the structural reconstruction process induced by the LOM is focused and the importance of multiple in situ/operando characterizations is highlighted to unveil the structural and chemical origins of the LOM. To conclude, a prospect on the remaining challenges and future opportunities for LOM electrocatalysts is presented.
Mitochondrial‐Targeted Copper Delivery for Cuproptosis‐Based Synergistic Cancer Therapy
Authors: Deng Jinpeng , Zhuang Huilan , Shao Sijie , Zeng Xuemei , Xue Panpan , Bai Tingjie , Wang Xiaoman , Shangguan Shijie , Chen Yuanchun , Yan Shuangqian , Huang Wei
Published: March 2024

Cuproptosis is dependent on mitochondrial respiration modulation by targeting lipoylated tricarboxylic acid cycle (TCA) cycle proteins, showing great potential in cancer treatment. However, the specific release of copper ions at mitochondrial is highly needed and still a major challenge to trigger cellular cuproptosis. Herein, a metal‐organic framework‐based nanoplatform (ZCProP) is designed for mitochondrial‐targeted and ATP/pH‐responsive Cu2+ and prodigiosin release. The released Cu2+ promotes aggregation of lipoylated protein and loss of Fe‐S cluster protein, resulting in cell cuproptosis. In the meanwhile, Cu2+ can concert with prodigiosin to induce mitochondrial dysfunction and DNA damage and enhance cell cuproptosis. Furthermore, this nanoplatform has an ability to deplete glutathione, which not only further promotes cuproptosis but also triggers cell ferroptosis by the suppression of glutathione peroxidase 4, an anti‐ferroptosis protein. Collectively, the designed ZCProP nanoplatform can responsively release cargos at mitochondrial and realize a conspicuous therapeutic efficacy through a cuproptosis‐mediated concerted effect. Along with its excellent biocompatibility, this nanoplatform may provide a novel therapeutic modality paradigm to boost cancer therapeutic strategies based on cuproptosis.
Record‐Efficiency Printable Hole‐Conductor‐Free Mesoscopic Perovskite Solar Cells Enabled by the Multifunctional Schiff Base Derivative
Authors: Chen Kai , Xiao Xufeng , Liu Jiale , Qi Jianhang , Gao Qiaojiao , Ma Yongming , Cheng Yanjie , Mei Anyi , Han Hongwei
Published: March 2024

Tailoring multifunctional additives for performing interfacial modifications, improving crystallization, and passivating defects is instrumental for the fabrication of efficient and stable perovskite solar cells (PSCs). Here, a Schiff base derivative, (chloromethylene) dimethyliminium chloride (CDCl), is introduced as an additive to modify the interface between the mesoporous TiO2 electron transport layer and the MAPbI3 light absorber during the annealing process. CDCl chemically links to TiO2 and MAPbI3 through coordination and hydrogen bonding, respectively, and results in the construction of fast electron extraction channels. CDCl also optimizes the energy‐level alignment of the TiO2/MAPbI3 heterojunction and improves the pore‐filling and crystallization of MAPbI3 in the mesoscopic scaffold, which inhibits nonradiative recombination and eliminates open‐circuit voltage losses. As a result, an impressive power conversion efficiency of 19.74%, which is the best one ever reported, is obtained for printable carbon‐based hole‐conductor‐free PSCs based on MAPbI3.
Rapid Phenotypic Antibiotics Susceptibility Analysis by a 3D Printed Prototype
Authors: Riester Oliver , Kaiser Lars , Laufer Stefan , Deigner Hans‐Peter
Published: March 2024

One of the most important public health concerns is the increase in antibiotic‐resistant pathogens and corresponding treatment of associated infections. Addressing this challenge requires more efficient use of antibiotics, achievable by the use of evidence‐based, effective antibiotics identified by antibiotic susceptibility testing (AST). However, the current standard method of phenotypic AST used for this purpose requires 48 h or more from sample collection to result. Until results are available, broad‐spectrum antibiotics are used to avoid delaying treatment. The turnaround time must therefore be shortened in order for the results to be available before the second administration of antibiotics. The phenotypic electrochemical AST method presented here identifies effective antibiotics within 5–10 h after sampling. Spiked serum samples, including polymicrobial samples, with clinically relevant pathogens and respective concentrations commonly found in bloodstream infections (Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, and Pseudomonas aeruginosa) are used. Direct loading of the test with diluted serum eliminates the need for a pre‐culture, as required by existing methods. Furthermore, by combining several electrochemical measurement procedures with computational analysis, allowing the method to be used both online and offline, the AST achieves a sensitivity of 94.44% and a specificity of 95.83% considering each replicate individually.
All‐Trans‐Retinoic Acid‐Adjuvanted mRNA Vaccine Induces Mucosal Anti‐Tumor Immune Responses for Treating Colorectal Cancer
Authors: Li Wei , Li Yijia , Li Jingjiao , Meng Junli , Jiang Ziqiong , Yang Chen , Wen Yixing , Liu Shuai , Cheng Xingdi , Mi Shiwei , zhao Yuanyuan , Miao Lei , Lu Xueguang
Published: March 2024

Messenger RNA (mRNA) cancer vaccines are a new class of immunotherapies that can activate the immune system to recognize and destroy cancer cells. However, their effectiveness in treating colorectal cancer located on the mucosal surface of the gut is limited due to the insufficient activation of mucosal immune response and inadequate infiltration of cytotoxic T cells into tumors. To address this issue, a new mRNA cancer vaccine is developed that can stimulate mucosal immune responses in the gut by co‐delivering all‐trans‐retinoic acid (ATRA) and mRNA using lipid nanoparticle (LNP). The incorporation of ATRA has not only improved the mRNA transfection efficiency of LNP but also induced high expression of gut‐homing receptors on vaccine‐activated T cells. Additionally, the use of LNP improves the aqueous solubility of ATRA, eliminating the need for toxic solvents to administer ATRA. Upon intramuscular injections, ATRA‐adjuvanted mRNA‐LNP significantly increase the infiltration of antigen‐specific, cytotoxic T cells in the lamina propria of the intestine, mesenteric lymph nodes, and orthotopic colorectal tumors, resulting in significantly improved tumor inhibition and prolonged animal survival compared to conventional mRNA‐LNP without ATRA. Overall, this study provides a promising approach for improving the therapeutic efficacy of mRNA cancer vaccines against colorectal cancer.
Crossbreeding Effect of Chalcogenation and Iodination on Benzene Additives Enables Optimized Morphology and 19.68% Efficiency of Organic Solar Cells
Authors: Zhou Tao , Jin Wenwen , Li Yinfeng , Xu Xiaopeng , Duan Yuwei , Li Ruipeng , Yu Liyang , Peng Qiang
Published: March 2024

Volatile solid additives have attracted increasing attention in optimizing the morphology and improving the performance of currently dominated non‐fullerene acceptor‐based organic solar cells (OSCs). However, the underlying principles governing the rational design of volatile solid additives remain elusive. Herein, a series of efficient volatile solid additives are successfully developed by the crossbreeding effect of chalcogenation and iodination for optimizing the morphology and improving the photovoltaic performances of OSCs. Five benzene derivatives of 1,4‐dimethoxybenzene (DOB), 1‐iodo‐4‐methoxybenzene (OIB), 1‐iodo‐4‐methylthiobenzene (SIB), 1,4‐dimethylthiobenzene (DSB) and 1,4‐diiodobenzene (DIB) are systematically studied, where the widely used DIB is used as the reference. The effect of chalcogenation and iodination on the overall property is comprehensively investigated, which indicates that the versatile functional groups provided various types of noncovalent interactions with the host materials for modulating the morphology. Among them, SIB with the combination of sulphuration and iodination enabled more appropriate interactions with the host blend, giving rise to a highly ordered molecular packing and more favorable morphology. As a result, the binary OSCs based on PM6:L8‐BO and PBTz‐F:L8‐BO as well as the ternary OSCs based on PBTz‐F:PM6:L8‐BO achieved impressive high PCEs of 18.87%, 18.81% and 19.68%, respectively, which are among the highest values for OSCs.
A Single‐Step Cleaning Process for Simultaneous Removal of Surface Impurities and Passivation of Sub‐Surface Defects in Perovskite Solar Cells
Authors: Cai Wanxian , Wang Yudi , Li Wenzhe , Yin Yanfeng , Liu Jing , Cai Wanqing , Wang Shuhong , Guo Jingya , Chang Shuai , Li Shukui , Wang Xiuyun , Shi Yantao
Published: March 2024

Perovskite solar cells (PSCs) suffer from the presence of non‐active and metastable species on the surface of solution‐processed perovskite films, and their adverse effects on charge extraction and long‐term stability cannot be fully addressed by conventional surface passivation strategies. In this study, a novel concept is proposed to achieve both precise removal of surface impurities and effective passivation of sub‐surface defects in a single step, utilizing a functional polymer‐based cleaning strategy. The moderate intermolecular force provided by the functional polymer and their inherent robust interchain interactions enable effective surface cleaning without disturbing the active crystal lattice. Following surface cleaning, the electron‐donating groups (C═O) in the polymer passivate the uncoordinated Pb2+ defects at the sub‐surface level. This synergistic effect of surface cleaning and sub‐surface defect passivation leads to a drastic reduction in interfacial non‐radiative recombination, elimination of ion migration pathways, and prevention of triggers for photodegradation. As a result, the power conversion efficiency (PCE) significantly improved from 22.84% to 25.51%, accompanied by a remarkable enhancement in operational stability. Moreover, the operability and effectiveness of this approach make it highly suitable for scaling up perovskite solar modules in the future.
Capuchin monkeys' (Sapajus [Cebus] apella) categorization of photos of unknown male conspecifics suggests attention to fWHR and a dominance bias
Authors: Meacham Ashley M. , Sosnowski Meghan J. , Kleider‐Offutt Heather M. , Brosnan Sarah F.
Published: March 2024

The ability to quickly perceive others' rank minimizes costs by helping individuals behave appropriately when interacting with strangers. Indeed, humans and at least some other species can quickly determine strangers' rank or dominance based only on physical features without observing others' interactions or behavior. Nonhuman primates can determine strangers' ranks by observing their interactions, and some evidence suggests that at least some cues to dominance, such as facial width‐to‐height ratio (fWHR), are also present in other primates. However, it is unknown whether they can determine strangers' rank simply by looking at their faces, rather than observing their interactions. If so, this would suggest selective pressure across the primates on both cues to dominance and the ability to detect those cues accurately. To address this, we examined the ability of male and female tufted capuchin monkeys (Sapajus [Cebus] apella) to categorize images of the faces of unknown conspecifics (Sapajus from different colonies) and humans (computer‐generated and real) as dominant or nondominant based only on still images. Capuchins' categorization of unknown conspecific faces was consistent with fWHR, a cue to dominance, although there was a strong tendency to categorize strangers as dominant, particularly for males. This was true despite the continued correct categorization of known individuals. In addition, capuchins did not categorize human strangers in accordance with external pre‐ratings of dominance by independent human raters, despite the availability of the same cue, fWHR. We consider these results in the context of capuchin socio‐ecology and what they mean for the evolution of rapid decision‐making in social contexts.
Real‐World Healthcare Cost Savings and Reduced Relapse Rate with Off‐Label Rituximab versus Disease‐Modifying Treatments Approved for Relapsing–Remitting Multiple Sclerosis: A Nationwide Cost‐Effectiveness Study
Authors: Alping Peter , Neovius Martin , Piehl Fredrik , Frisell Thomas
Published: March 2024

Objective

Although off‐label use of rituximab is a common alternative to disease‐modifying therapies (DMTs) approved for multiple sclerosis (MS) in several countries, the impact of this on treatment cost‐effectiveness is not well known.

Methods

We evaluated the relative cost‐effectiveness of rituximab and MS‐approved DMTs in a register‐based cohort study of Swedish residents with relapsing–remitting MS, aged 18–65 years, starting treatment with rituximab, natalizumab, fingolimod, or dimethyl fumarate between January 2010 and July 2016, and followed through July 2021 (n = 5,924). By linking the population‐based Swedish MS register to several Swedish health care and demographic registers, we estimated health care costs in relation to number of relapses, over 5 years from treatment start. Differences between treatments were estimated in inverse probability of treatment‐weighted regression models, adjusting for a broad range of potential confounders covering demographics, medical history, and MS‐related clinical characteristics.

Results

Off‐label rituximab was associated with both lower total health care costs (mean cost savings ranged $35,000–$66,000 vs. each approved DMT), and fewer relapses (mean number of prevented relapses ranged 0.12–0.22), per started therapy over 5 years. Results were robust to variations in discounting and pricing of health care visits, with the main driver of cost‐savings being the price of the index drug itself.

Interpretation

The cost‐effectiveness of rituximab dominated the MS‐approved alternatives. Off‐label, low‐dose rituximab should be considered for persons with MS and could reduce barriers to treatment, especially in resource‐limited settings. ANN NEUROL 2024;95:1099–1111
Superoxide Radicals in Uranyl Peroxide Solids: Lasting Signatures Identified by Electron Paramagnetic Resonance Spectroscopy
Authors: Scherrer Sarah K. , Gates Cassandra , Rajapaksha Harindu , Greer Samuel M. , Stein Benjamin W. , Forbes Tori Z.
Published: March 2024

U(VI) peroxide phases (studtite and meta‐studtite) are found throughout the nuclear fuel cycle and exist as corrosion products in high radiation fields. Peroxides are part of a family of reactive oxygen species (ROS) that include hydroperoxyl and superoxide species and are produced during alpha radiolysis of water. While U(VI) peroxides have been thoroughly investigated, the incorporation and stability of ROS species within studtite have not been validated. In the current study, electron paramagnetic resonance (EPR) spectroscopy was used to identify the presence of free radicals within a series of U(VI) peroxide samples containing depleted, highly enriched, and natural uranium. Density functional theory calculations indicated that the predicted EPR signals matched well with a superoxide (O2−⋅) species incorporated into the studtite structure, confirming the presence of ROS in the material. Further analysis of samples that were synthesized between 1945 and 2023 indicated that there is a correlation between the radical signal and the product of specific activity multiplied by age of the sample.
Protein‐Integrated Hydrogen‐Bonded Organic Frameworks: Chemistry and Biomedical Applications
Authors: Li Lijuan , Ma Tianyu , Wang Ming
Published: March 2024

Hydrogen‐bonded organic frameworks (HOFs) are porous nanomaterials that offer exceptional biocompatibility and versatility for integrating proteins for biomedical applications. This minireview concisely discusses recent advancements in the chemistry and functionality of protein‐HOF interfaces. It particularly focuses on strategic methodologies, such as the careful selection of building blocks and the genetic engineering of proteins, to facilitate protein‐HOF interactions. We examine the role of enzyme encapsulation within HOFs, highlighting its capability to preserve enzyme function, a crucial aspect for applications in biosensing and disease diagnosis. Moreover, we discuss the emerging utility of nanoscale HOFs for intracellular protein delivery, illustrating their applicability as nanoreactors for intracellular catalysis and neuroprotective biorthogonal catalysis within cellular compartments. We highlight the significant advancement of designing biodegradable HOFs tailored for cytosolic protein delivery, underscoring their promising application in targeted cancer therapies. Finally, we provide a perspective viewpoint on the design of biocompatible protein‐HOF assemblies, underlining their promising prospects in drug delivery, disease diagnosis, and broader biomedical applications.
Bioinspired Synthesis of Allysine for Late‐Stage Functionalization of Peptides
Authors: Emenike Benjamin , Shahin Sophia , Raj Monika
Published: March 2024

Inspired by the enzyme lysyl oxidase, which selectively converts the side chain of lysine into allysine, an aldehyde‐containing post‐translational modification, we report herein the first chemical method for the synthesis of allysine by selective oxidation of dimethyl lysine. This approach is highly chemoselective for dimethyl lysine on proteins. We highlight the utility of this biomimetic approach for generating aldehydes in a variety of pharmaceutically active linear and cyclic peptides at a late stage for their diversification with various affinity and fluorescent tags. Notably, we utilized this approach for generating small‐molecule aldehydes from the corresponding tertiary amines. We further demonstrated the potential of this approach in generating cellular models for studying allysine‐associated diseases.
Bending, Twisting, and Propulsion of Photoreactive Crystals by Controlled Gas Release
Authors: Yu Chunjiao , Jiang Xiaofan , Al‐Handawi Marieh B. , Naumov Panče , Li Liang , Yu Qi , Wang Guoming
Published: March 2024

The rapid release of gas by a chemical reaction to generate momentum is one of the most fundamental ways to elicit motion that could be used to sustain and control the motility of objects. We report that hollow crystals of a three‐dimensional supramolecular metal complex that releases gas by photolysis can propel themselves or other objects and advance in space when suspended in mother solution. In needle‐like regular crystals, the reaction occurs mainly on the surface and results in the formation of cracks that evolve due to internal pressure; the expansion on the cracked surface of the crystal results in bending, twisting, or coiling of the crystal. In hollow crystals, gas accumulates inside their cavities and emanates preferentially from the recess at the crystal terminus, propelling the crystals to undergo directional photomechanical motion through the mother solution. The motility of the object which can be controlled externally to perform work delineates the concept of “crystal microbots”, realized by photoreactive organic crystals capable of prolonged directional motion for actuation or delivery. Within the prospects, we envisage the development of a plethora of light‐weight, efficient, autonomously operating robots based on organic crystals with high work capacity where motion over large distances can be attained due to the large volume of latent gas generated from a small volume of the crystalline solid.
A Cytochrome P450 Catalyzes Oxidative Coupling Formation of Insecticidal Dimeric Indole Piperazine Alkaloids
Authors: He Qian , Zhang Hua‐Ran , Zou Yi
Published: March 2024

Cytochrome P450 (CYP450)‐catalyzed oxidative coupling is an efficient strategy for using simple building blocks to construct complex structural scaffolds of natural products. Among them, heterodimeric coupling between two different monomers is relatively scarce, and the corresponding CYP450s are largely undiscovered. In this study, we discovered a fungal CYP450 (CpsD) and its associated cps cluster from 37208 CYP450s of Pfam PF00067 family member database and subsequently identified a group of new skeleton indole piperazine alkaloids (campesines A−G) by combination of genome mining and heterologous synthesis. Importantly, CYP450 CpsD mainly catalyzes intermolecular oxidative heterocoupling of two different indole piperazine monomers to generate an unexpected 6/5/6/6/6/6/5/6 eight‐ring scaffold through the formation of one C−C bond and two C−N bonds, illuminating its first dimerase role in this family of natural products. The proposed catalytic mechanism of CpsD was deeply investigated by diversified substrate derivatization. Moreover, dimeric campesine G shows good insecticidal activity against the global honeybee pest Galleria mellonella. Our study shows a representative example of discovering new skeleton monomeric and dimeric indole piperazine alkaloids from microbial resources, expands our knowledge of bond formation by CYP450s and supports further development of the newly discovered and engineered campesine family compounds as potential biopesticides.
Hydrogen‐Bonded Organic Framework Supporting Atomic Bi−N2O2 Sites for High‐Efficiency Electrocatalytic CO2 Reduction
Authors: Wang Changli , Lv Zunhang , Liu Yarong , Liu Rui , Sun Caiting , Wang Jinming , Li Liuhua , Liu Xiangjian , Feng Xiao , Yang Wenxiu , Wang Bo
Published: March 2024

Single atomic catalysts (SACs) offer a superior platform for studying the structure–activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to obtain well‐defined and novel site configuration owing to the uncertainty of functional framework‐derived SACs through calcination. Herein, a novel Bi−N2O2 site supported on the (1 1 0) plane of hydrogen‐bonded organic framework (HOF) is reported directly for CO2RR. In flow cell, the target catalyst Bi1‐HOF maintains a faradaic efficiency (FE) HCOOH of over 90 % at a wide potential window of 1.4 V. The corresponding partial current density ranges from 113.3 to 747.0 mA cm−2. And, Bi1‐HOF exhibits a long‐term stability of over 30 h under a successive potential‐step test with a current density of 100–400 mA cm−2. Density function theory (DFT) calculations illustrate that the novel Bi−N2O2 site supported on the (1 1 0) plane of HOF effectively induces the oriented electron transfer from Bi center to CO2 molecule, reaching an enhanced CO2 activation and reduction. Besides, this study offers a versatile method to reach series of M−N2O2 sites with regulable metal centers via the same intercalation mechanism, broadening the platform for studying the structure–activity relationships during CO2RR.
Large‐Area Ultrathin Metal–Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations
Authors: Liang Yueyao , Zhang Zhengqing , Chen Aibing , Yu Caijiao , Sun Yuxiu , Du Juan , Qiao Zhihua , Wang Zhi , Guiver Michael D. , Zhong Chongli
Published: March 2024

Ultrathin continuous metal–organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic‐imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large‐area fabrication. Here, we propose a ligand back diffusion‐assisted bipolymer‐directed metal ion distribution strategy for preparing large‐area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross‐linked two‐dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large‐area ultrathin MOF membranes. We report the practical fabrication of three representative defect‐free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50–130 nm), including ZIFs and carboxylate‐linker MOFs. Among these, the ZIF‐8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale‐up practicality, MOF membranes were prepared and incorporated into spiral‐wound membrane modules with an active area of 4,800 cm2. The ZIF‐8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).
Stepwise Dissipative Control of Multimodal Motion in a Silver(I) Catenate
Authors: Elramadi Emad , Kundu Sohom , Mondal Debabrata , Paululat Thomas , Schmittel Michael
Published: March 2024

Stepwise dissipative control of two distinct motions, i.e., shuttling and sliding, is demonstrated in a single multicomponent device. When [2]rotaxane 1, which acts as a biped, and deck 2 were treated with AgBF4/PhCH2Br+NEt3 as chemical fuel, the transient catenate [Ag(1)]+ ⋅ [Ag3(2)]3+ was instantly generated showing multimodal motion and autonomous return to 1 and 2. In the dissipative process, catenate [Ag(1)]+ ⋅ [Ag3(2)]3+ cleanly transformed into the follow‐up transient device (1) ⋅ [Ag3(2)]3+ exhibiting only sliding motion. Two interference‐free dissipative cycles proved the resilience and robustness of the process.
Orthogonal Photoswitching in a Porous Organic Framework
Authors: Sheng Jinyu , Perego Jacopo , Bracco Silvia , Cieciórski Piotr , Danowski Wojciech , Comotti Angiolina , Feringa Ben L.
Published: March 2024

The development of photoresponsive systems with non‐invasive orthogonal control by distinct wavelengths of light is still in its infancy. In particular, the design of photochemically triggered‐orthogonal systems integrated into solid materials that enable multiple dynamic control over their properties remains a longstanding challenge. Here, we report the orthogonal and reversible control of two types of photoswitches in an integrated solid porous framework, that is, visible‐light responsive o‐fluoroazobenzene and nitro‐spiropyran motifs. The properties of the constructed material can be selectively controlled by different wavelengths of light thus generating four distinct states providing a basis for dynamic multifunctional materials. Solid‐state NMR spectroscopy demonstrated the selective transformation of the azobenzene switch in the bulk, which in turn modulates N2 and CO2 adsorption.