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Understanding the water-involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water-promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water-dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO-SnO2 imparts water-resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water-promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C-H and C-C cleavage. Consequently, the tailored CoO-C-SnO2 showcases a remarkable 60-fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high-humidity conditions.
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BACKGROUND: Managing persistent elbow instability and chronic dislocations presents challenges despite traditional treatments. Supplementary methods like immobilization and various fixations, though common, can carry high complication rates. This study assesses the efficacy of bridge plating in treating complex elbow instability through a retrospective review of patients. Data on characteristics, treatment duration, range of motion, complications, and evaluation scores were analyzed, providing insights into outcomes complications associated with bridge plating. RESULTS: Eleven patients were reviewed at a mean follow-up of 80 ± 68 weeks postoperatively. The mean age was 53 ± 14 years and there were 5 females and 6 males. The mean body mass index was 38. Bridge plating was used for a spectrum of complex elbow injuries. The mean time from injury to bridge plating in acute cases was 29 ± 19 days and 344 ± 381 days in chronic cases. The mean duration of bridge plating was 121 ± 72 days. At the time of plate removal, mean intraoperative elbow motion was extension 58° ± 12°, flexion 107° ± 14°, supination 66° ± 23° and pronation 60° ± 26°. At the latest follow-up visit, mean elbow motion was extension 37° ± 22°, flexion 127° ± 17°, supination 72° ± 15°, and pronation 63° ± 18°. There were 6 complications (55%): heterotopic ossification, ulnar neuropathy, wound failure over the plate in a thin patient, an ulnar shaft periprosthetic fracture due to a seizure-induced fall, and persistent elbow subluxation despite bridge plate fixation. Finally, 1 patient sustained a fracture of a 3.5-mm locking bridge plate. One patient required a contracture release for persistent stiffness. Four of these complications can be directly attributed to the use of the bridge plate (36%). At final follow-up, the mean patient-rated elbow evaluation score was 34, with 0 indicating no pain and disability. The mean Single Assessment Numeric Evaluation score was 66% for the 8 patients who had this available, with 100% being the best possible attainable score. CONCLUSION: Bridge plating effectively maintains joint reduction in selected complex elbow instability cases. However, patients with bridge plates often require a second surgery for removal and experience high rates of general complications because of the complexity of their condition.
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Placas Óseas , Articulación del Codo , Inestabilidad de la Articulación , Rango del Movimiento Articular , Humanos , Masculino , Femenino , Persona de Mediana Edad , Estudios Retrospectivos , Inestabilidad de la Articulación/cirugía , Articulación del Codo/cirugía , Adulto , Anciano , Lesiones de Codo , Resultado del Tratamiento , Estudios de Seguimiento , Luxaciones Articulares/cirugía , Fijación Interna de Fracturas/métodos , Fijación Interna de Fracturas/instrumentaciónRESUMEN
Background: Current commercial elbow braces have a straight hinge that does not account for the native carrying angle of the elbow. The objective of this study was to determine the effectiveness of a custom-designed hinged elbow orthosis (HEO) with variable valgus angulations in stabilizing a lateral collateral ligament (LCL) deficient elbow. Methods: Eight cadaveric upper extremities were mounted in an elbow motion simulator in the abducted varus gravity-loaded position. The specimens were examined before and after simulated LCL injury and then with the addition of the custom-designed HEO with 0°, 10°, and 20° of valgus angulation. Kinematic data were recorded using an electromagnetic tracking system. Results: The LCL injured state with or without the brace resulted in significant increases in varus angulation of the elbow compared to the intact state in both pronation and supination (P < 0.05). There were no significant differences in varus-valgus angulation or ulnohumeral rotation between any of the brace angles and the LCL injured state with the forearm pronated and supinated. Discussion: The custom-designed HEO did not provide any additional stability to the LCL injured elbow. The varus arm position should be avoided during the rehabilitation of an LCL injured elbow even when an HEO is used.
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The global expansion of rapeseed seed quality has been focused on maintaining glucosinolate (GSL) and erucic acid (EA) contents. However, the influence of seed GSL and EA contents on the germination process under drought stress remains poorly understood. Herein, 114 rapeseed accessions were divided into four groups based on GSL and EA contents to investigate their performance during seed imbibition under drought stress. Our results revealed significant variations in seed germination-related traits, particularly with higher GSL and EA, which exhibited higher germination % (G%) and lower mean germination time (MGT) under drought stress conditions. Moreover, osmoregulation, enzymatic system and hormonal regulation were improved in high GSL and high EA (HGHE) versus low GSL and low EA (LGLE) seeds, indicating the essential protective role of GSL and EA during the germination process in response to drought stress. The transcriptional regulation mechanism for coordinating GSL-EA-related pathways in response to drought stress during seed imbibition was found to involve the differential expression of sugar metabolism-, antioxidant-, and hormone-related genes with higher enrichment in HGHE compared to LGLE seeds. GO enrichment analysis showed higher variations in transcription regulator activity and DNA-binding transcription factors, as well as ATP and microtubule motor activity in GSL-EA-related pathways. Furthermore, KEGG analysis identified cellular processes, environmental information processing, and metabolism categories, with varied gene participation between GSL, EA and GSL-EA-related pathways. For further clarification, QY7 (LGLE) seeds were primed with different concentrations of GSL and EA under drought stress conditions. The results showed that 200 µmol/L of GSL and 400 µmol/L of EA significantly improved G%, MGT, and seedling fresh weight, besides regulating stress and fatty acid responsive genes during the seed germination process under drought stress conditions. Conclusively, exogenous application of GSL and EA is considered a promising method for enhancing the drought tolerance of LGLE seeds. Furthermore, the current investigation could provide a theoretical basis of GSL and EA roles and their underlying mechanisms in stress tolerance during the germination process.
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Brassica napus , Brassica rapa , Ácidos Erucicos , Germinación/genética , Brassica napus/genética , Glucosinolatos/metabolismo , Sequías , Semillas/genética , Semillas/metabolismo , Brassica rapa/genética , Perfilación de la Expresión GénicaRESUMEN
The recently surged halide-based solid electrolytes (SEs) are great candidates for high-performance all-solid-state batteries (ASSBs), due to their decent ionic conductivity, wide electrochemical stability window, and good compatibility with high-voltage oxide cathodes. In contrast to the crystalline phases in halide SEs, amorphous components are rarely understood but play an important role in Li-ion conduction. Here, we reveal that the presence of amorphous component is common in halide-based SEs that are prepared via mechanochemical method. The fast Li-ion migration is found to be associated with the local chemistry of the amorphous proportion. Taking Zr-based halide SEs as an example, the amorphization process can be regulated by incorporating O, resulting in the formation of corner-sharing Zr-O/Cl polyhedrons. This structural configuration has been confirmed through X-ray absorption spectroscopy, pair distribution function analyses, and Reverse Monte Carlo modeling. The unique structure significantly reduces the energy barriers for Li-ion transport. As a result, an enhanced ionic conductivity of (1.35 ± 0.07) × 10-3 S cm-1 at 25 °C can be achieved for amorphous Li3ZrCl4O1.5. In addition to the improved ionic conductivity, amorphization of Zr-based halide SEs via incorporation of O leads to good mechanical deformability and promising electrochemical performance. These findings provide deep insights into the rational design of desirable halide SEs for high-performance ASSBs.
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All-solid-state lithium metal batteries can address crucial challenges regarding insufficient battery cycling life and energy density. The demonstration of long-cycling dendrite-free all-solid-state lithium metal batteries requires precise tailoring of lithium-ion transport of solid-state electrolytes (SSEs). In this work, a proof of concept is reported for precise tailoring of lithium-ion transport of a halide SSE, Li3InCl6, including intragranular (within grains) but also intergranular (between grains) lithium-ion transport. Lithium-ion migration tailoring mechanism in crystals is developed by unexpected enhanced Li, In, and Cl vacancy populations and lower energy barrier for hopping. The lithium-ion transport tailoring mechanism between the grains is determined by the elimination of voids between grains and the formation of unexpected supersonic conducting grain boundaries, boosting the lithium dendrite suppression ability of SSE. Due to boosted lithium-ion conduction and dendrite-suppression ability, the all-solid-state lithium metal batteries coupled with Ni-rich LiNi0.83Co0.12Mn0.05O2 cathodes and lithium metal anodes demonstrate breakthroughs in electrochemical performance by achieving extremely long cycling life at a high current density of 0.5 C (2000 cycles, 93.7% capacity retention). This concept of precise tailoring of lithium-ion transport provides a cost, time, and energy efficient solution to conquer the remaining challenges in all-solid-state lithium-metal batteries for fast developing electric vehicle markets.
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Attaining substantial areal capacity (>3 mAh/cm2) and extended cycle longevity in all-solid-state lithium metal batteries necessitates the implementation of solid-state electrolytes (SSEs) capable of withstanding elevated critical current densities and capacities. In this study, we report a high-performing vacancy-rich Li9N2Cl3 SSE demonstrating excellent lithium compatibility and atmospheric stability and enabling high-areal capacity, long-lasting all-solid-state lithium metal batteries. The Li9N2Cl3 facilitates efficient lithium-ion transport due to its disordered lattice structure and presence of vacancies. Notably, it resists dendrite formation at 10 mA/cm2 and 10 mAh/cm2 due to its intrinsic lithium metal stability. Furthermore, it exhibits robust dry-air stability. Incorporating this SSE in Ni-rich LiNi0.83Co0.11Mn0.06O2 cathode-based all-solid-state batteries, we achieve substantial cycling stability (90.35% capacity retention over 1500 cycles at 0.5 C) and high areal capacity (4.8 mAh/cm2 in pouch cells). These findings pave the way for lithium metal batteries to meet electric vehicle performance demands.
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Model species continue to underpin groundbreaking plant science research. At the same time, the phylogenetic resolution of the land plant Tree of Life continues to improve. The intersection of these two research paths creates a unique opportunity to further extend the usefulness of model species across larger taxonomic groups. Here we promote the utility of the Arabidopsis thaliana model species, especially the ability to connect its genetic and functional resources, to species across the entire Brassicales order. We focus on the utility of using genomics and phylogenomics to bridge the evolution and diversification of several traits across the Brassicales to the resources in Arabidopsis, thereby extending scope from a model species by establishing a "model clade". These Brassicales-wide traits are discussed in the context of both the model species Arabidopsis thaliana and the family Brassicaceae. We promote the utility of such a "model clade" and make suggestions for building global networks to support future studies in the model order Brassicales.
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BACKGROUND: The aim of this study was to determine the optimal repair tension of the lateral collateral ligament of the elbow by performing simulated active flexion with the arm in the varus gravity loaded position using an in vitro elbow simulator. METHODS: Eight cadaveric specimens were mounted in the varus gravity loaded orientation onto an elbow motion simulator. Four states were studied (intact, lateral collateral ligament injured, and 15 N and 20 N lateral collateral ligament repairs) with the forearm in supination and pronation. An electromagnetic tracking system was used to measure joint kinematics during active elbow flexion. FINDINGS: There was no difference in ulnohumeral rotation between the intact state and the 15 N repair (P = .150 for pronation; P = 1.0 for supination) or the 20 N repair (P = 1.0 for pronation; P = .568 for supination). For varus-valgus angulation, the 20 N repair was not statistically different from the intact state (P = .059 in pronation; P = 1.0 in supination). INTERPRETATION: Repair of the lateral collateral ligament following injury can restore joint kinematics with the arm in the varus position. A repair tension of 20 N was successful in restoring joint stability for simulated active motion with the forearm in pronation and supination. This study shows that when the lateral collateral ligament is repaired with adequate tension, avoidance of the varus position may not be as crucial during early motion.
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Ligamentos Colaterales , Articulación del Codo , Inestabilidad de la Articulación , Ligamentos Laterales del Tobillo , Humanos , Codo/cirugía , Cadáver , Ligamentos Colaterales/cirugía , Articulación del Codo/cirugía , Fenómenos Biomecánicos , Rango del Movimiento ArticularRESUMEN
As one of the promising sustainable energy storage systems, academic research on rechargeable Zn-air batteries has recently been rejuvenated following development of various 3d-metal electrocatalysts and identification of their dynamic reconstruction toward (oxy)hydroxide, but performance disparity among catalysts remains unexplained. Here, this uncertainty is addressed through investigating the anionic contribution to regulate dynamic reconstruction and battery behavior of 3d-metal selenides. Comparing with the alloy counterpart, anionic chemistry is identified as a performance promoter and further exploited to empower Zn-air batteries. Based on theoretical modeling, Se-resolved operando spectroscopy, and advanced electron microscopy, a three-step Se evolution is established, consisting of oxidation, leaching, and recoordination. The process generates an amorphous (oxy)hydroxide with O-sharing bonded Se motifs that triggers charge redistribution at metal sites and lowers the energetic barrier of their current-driven redox. A pervasive concept of Se back-feeding is then proposed to describe the underlying chemistry for 3d-metal selenides with diversity in crystals or compositions, and the feasibility to fine-tune their behavior is also presented.
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In an experiment combining various approaches, a precise examination of a portion of the phase diagram of a CsF-Al2O3 system was carried out up to 40 mol% Al2O3. CsF-Al2O3 solidified mixtures have been investigated using high-field solid-state NMR (133Cs, 27Al, and 19F) spectroscopy and X-ray powder diffraction over a broad range of compositions with synchrotron powder diffraction and Rietveld analysis. A new cesium oxo-fluoro-aluminate, Cs2Al2O3F2, was discovered, prepared, and structurally analyzed by synchrotron diffraction analysis. In addition to Cs2Al2O3F2, we have synthesized the following pure compounds in order to aid in the interpretation of NMR spectra of the solidified samples: CsAlF4, Cs3AlF6, and CsAlO2.
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Background The Tolat sigmoid notch classification is a commonly used classification to characterize the distal radioulnar joint (DRUJ). This classification was based on a limited assessment of the entire joint, which may lead to inaccuracies in sigmoid notch evaluation. Questions/Purposes The purpose of this study is to assess the reliability of the Tolat classification for sigmoid notch characterization. Methods The sigmoid notch of 52 models of cadaveric forearms was assessed by applying the Tolat classification to the three-dimensional (3D) modeled notch and then slices at the start of the notch (0 mm) and 4 mm more proximal. The inter- and intrarater agreement was assessed using Cohen's and Fleiss' kappa statistic. Results Agreement between iterations regardless of slices or surgeons/radiologists was moderate. Intrarater agreement between pairs of slices (0 vs 4 mm, 0 mm vs 3D, 4 mm vs 3D) was moderate, whereas agreement between all slices was slight. Agreement between surgeons and between radiologists was moderate, while agreement across all raters and slices was fair. Models described as "other" were more consistent in 3D classifications and were commonly classified as a reverse ski slope. Conclusions Classification using the Tolat scheme is fair to moderate at best. Classification of the sigmoid notch using an axial view of the distal radius may not accurately reflect the anatomy throughout the notch. Clinical Relevance The Tolat classification supplies a limited analysis of the sigmoid notch, and does not represent a comprehensive evaluation of the entire joint. Future classification systems should characterize the entire sigmoid notch.
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BACKGROUND: Heterotopic ossification is a frequent complication following surgical treatment of elbow trauma. The use of indomethacin to prevent heterotopic ossification is reported in the literature; however, its effectiveness is controversial. The purpose of this randomized, double-blind, placebo-controlled study was to determine whether indomethacin is effective in reducing the incidence and severity of heterotopic ossification after surgical management of elbow trauma. METHODS: Between February 2013 and April 2018, 164 eligible patients were randomized to receive postoperative indomethacin or placebo medication. The primary outcome was the incidence of heterotopic ossification on elbow radiographs at 1-year follow-up. Secondary outcomes included the Patient Rated Elbow Evaluation score, Mayo Elbow Performance Index score, and Disabilities of the Arm, Shoulder and Hand score. Range of motion, complications, and nonunion rates were also obtained. RESULTS: At 1-year follow-up, there was no significant difference in the incidence of heterotopic ossification between the indomethacin group (49%) and the control group (55%) (relative risk, 0.89; P = .52). There were no significant differences in postoperative Patient Rated Elbow Evaluation, Mayo Elbow Performance Index, and Disabilities of the Arm, Shoulder and Hand scores or range of motion (P = .16). The complication rate was 17% in both the treatment and control groups (P > .99). There were no nonunions in either group. CONCLUSION: This Level I study demonstrated that indomethacin prophylaxis against heterotopic ossification in the setting of surgically treated elbow trauma was not significantly different from placebo.
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Traumatismos del Brazo , Articulación del Codo , Indometacina , Osificación Heterotópica , Humanos , Traumatismos del Brazo/complicaciones , Codo/cirugía , Articulación del Codo/cirugía , Indometacina/administración & dosificación , Indometacina/uso terapéutico , Osificación Heterotópica/prevención & control , Osificación Heterotópica/complicaciones , Rango del Movimiento Articular , Complicaciones PosoperatoriasRESUMEN
Background: In a simple isolated capitellar/trochlear fracture without extensive posterior comminution, arthroscopic reduction and internal fixation (ARIF) can provide an alternative option to open reduction internal fixation. The purpose of this retrospective case series was to report on the technique and outcomes of arthroscopic reduction and internal fixation of capitellar/trochlear fractures. Methods: All patients that underwent ARIF at a single upper extremity referral centre in the last twenty years were reviewed. Patient demographics, preoperative, intraoperative, and postoperative records were obtained through chart review and telephone followup. Results: Ten cases of ARIF were identified over a twenty year period performed by two surgeons. The average age of patients was 37 years (17-63 years), with nine females and one male. With an average followup of eight years, nine of ten patients had a mean range of motion from 0 to 142 degrees. Their average MEPI and PREE score were 93 ± 7 and 8 ± 14, respectively. Four patients had focal cartilage collapse with three that required a reoperation. There were no infections, nonunions, or arthroscopy related complications. Conclusion: ARIF offers an alternative to ORIF for capitellar/trochlear fractures producing good results while providing better visualization of the fracture reduction and minimizing soft tissue dissection.
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AIMS: In order to mitigate early hypoglycemia in preterm infants, some clinicians have recently explored interventions such as delivery room commencement of dextrose infusions or delivery room administration of buccal dextrose gel. This review aimed to systematically investigate the literature regarding the provision of delivery room (prior to admission) parenteral glucose as a method to reduce the risk of initial hypoglycemia (measured at the time of NICU admission blood testing) in preterm infants. MATERIALS AND METHODS: Using PRISMA guidelines a literature search (May 2022) was conducted using PubMed, Embase, Scopus, Cochrane Library, OpenGrey, and Prospero databases. The clinicaltrials.gov database was searched for possible completed/ongoing clinical trials. Studies that included moderate preterm (≤33+6 weeks) or younger birth gestations or very low birth weight (or smaller) infants, and that administered parenteral glucose in the delivery room were included. The literature was appraised via data extraction, narrative synthesis, and critical review of the study data. RESULTS: A total of five studies (published 2014-2022) were eligible for inclusion (three before-after "quasi-experimental" studies, one retrospective cohort study, and one case-control study). Most included studies used intravenous dextrose as the intervention. Individual study effects (odds ratios) favored the intervention in all included studies. It was felt that the low number of studies, the variability in study design, and the nonadjustment for confounding co-interventions (co-exposures) precluded a meta-analysis. Quality assessment of the studies revealed a spectrum of bias from low to high risk, however, most studies had moderate to high risk of bias, and their direction of bias favored the intervention. CONCLUSIONS: This extensive search and systematic appraisal of the literature indicates that there exists few studies (these are low grade and at moderate to high risk of bias) for the interventions of either intravenous or buccal dextrose given in the delivery room. It is not clear if these interventions impact on rates of early (NICU admission) hypoglycemia in these preterm infants. Obtaining intravenous access in the delivery room is not guaranteed and can be difficult in these small infants. Future research should consider various routes for commencing delivery room glucose in these preterm infants and should take the form of randomized controlled trials.
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Salas de Parto , Hipoglucemia , Recién Nacido , Lactante , Embarazo , Humanos , Femenino , Estudios de Casos y Controles , Recien Nacido Prematuro , Estudios Retrospectivos , Hipoglucemia/prevención & control , GlucosaRESUMEN
AIM: The aims of our awareness campaign were to increase the number of inquiries by patients to doctors for two new diabetes drugs funded by Pharmac on 1 February 2021 and 1 September 2021 respectively, to increase the number of applications for special authority, and to trial a "grass roots" community dissemination of information that appeals to explicit individual benefit from the new medicines. The campaign used an approach tailored primarily to the Pasifika community. METHODS: The campaign ran from April 2021 to July 2021 and targeted Counties Manukau communities using a talanoa approach by primarily by sharing key messages informally through social networks face-to-face by word-of-mouth. The key messages about the new medicines were shared orally with local organisations, family, friends, influential community leaders and colleagues such as justices of peace, kapa haka leaders, committee representatives from local schools, sports, cultural and hobby clubs. A printed pamphlet translated in Maori, Samoan, Tongan and English with the key messages was also distributed widely. The campaign notified 102 primary care practices, used Pacific equity teams to disseminate the information, promoted the message on Maori and Pasifika radio stations, and engaged a public relations company who contacted the South Auckland Community Trust, councillors, community boards and local churches. This approach was intended to spread the message through the community to reach people with type 2 diabetes and/or their families to prompt them to contact their doctor and see if they are eligible. To gauge how effective the campaign was, we gathered data from Pharmac that quantified new prescriptions for the new medicines by location and ethnicity. RESULTS: An estimated 45,000 people were exposed to our campaign materials or were told about the new medicines by people they knew. These estimations were conservatively based on the known membership, listenership, and reach of the various delivery arms by which this campaign was delivered. These data show Pacific patients, the focus of about 64% of our project work, were 40% more likely to apply and receive a prescription for empagliflozin in Counties Manukau than anywhere else in the country. CONCLUSION: Direct-to-consumer marketing is an effective way of increasing health awareness and uptake of newly funded diabetes medicine amongst Pacific patients with type 2 diabetes.
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Diabetes Mellitus Tipo 2 , Humanos , Diabetes Mellitus Tipo 2/tratamiento farmacológico , Nueva Zelanda , Hipoglucemiantes/uso terapéuticoRESUMEN
Glucosinolates (GSLs), found mainly in species of the Brassicaceae family, are one of the most well-studied classes of secondary metabolites. Produced by the action of myrosinase on GSLs, GSL-derived hydrolysis products (GHPs) primarily defend against biotic stress in planta. They also significantly affect the quality of crop products, with a subset of GHPs contributing unique food flavors and multiple therapeutic benefits or causing disagreeable food odors and health risks. Here, we explore the potential of these bioactive functions, which could be exploited for future sustainable agriculture. We first summarize our accumulated understanding of GSL diversity and distribution across representative Brassicaceae species. We then systematically discuss and evaluate the potential of exploited and unutilized genes involved in GSL biosynthesis, transport, and hydrolysis as candidate GSL engineering targets. Benefiting from available information on GSL and GHP functions, we explore options for multifunctional Brassicaceae crop ideotypes to meet future demand for food diversification and sustainable crop production. An integrated roadmap is subsequently proposed to guide ideotype development, in which maximization of beneficial effects and minimization of detrimental effects of GHPs could be combined and associated with various end uses. Based on several use-case examples, we discuss advantages and limitations of available biotechnological approaches that may contribute to effective deployment and could provide novel insights for optimization of future GSL engineering.