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It is crucial to rationally design and synthesize atomic-scale transition metal-doped carbon catalysts with high electrocatalytic activity to achieve a high-efficient oxygen reduction reaction (ORR). Herein, an electrocatalyst comprised of Fe-Fe dual atom pairs and N-doped concave carbon are reported (N-CC@Fe DA) that achieves ultrahigh electrocatalytic ORR activity. The catalyst is prepared by a gaseous doping approach, with zeolitic imidazolate framework-8 (ZIF-8) as the carbon framework precursor and cyclopentadienyliron dicarbonyl dimer as the Fe-Fe atom pair precursor. The catalyst exhibits high cathodic ORR catalytic performance in an alkaline Zn/air battery and proton exchange membrane fuel cell (PEMFC), yielding peak power densities of 241 mW cm-2 and 724 mW cm-2, respectively, compared to 127 mW cm-2 and 1.20 W cm-2 with conventional Pt/C catalysts as cathodes. The presence of Fe atom pairs coordinate with N atoms is revealed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analysis, and Density Functional Theory (DFT) calculation results show that the Fe-Fe pair structure is beneficial for adsorbing oxygen molecules, activating the OâO bond, and desorbing OH* intermediates formed during oxygen reduction, resulting in a more efficient oxygen reaction. The findings may provide a new pathway for preparing ultra-high-performance doped carbon catalysts with Fe-Fe atom pair structures.
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The practical implementation of lithium-sulfur batteries is severely hindered by the rapid capacity fading due to the solubility of the intermediate lithium polysulfides (LiPSs) and the sluggish redox kinetics. Herein, high-entropy metal nitride nanocrystals (HEMN) embedded within nitrogen-doped concave porous carbon (N-CPC) polyhedra are rationally designed as a sulfur host via a facile zeolitic imidazolate framework (ZIF)-driven adsorption-nitridation process toward this challenge. The configuration of high-entropy with incorporated metal manganese (Mn) and chromium (Cr) will optimize the d-band center of active sites with more electrons occupied in antibonding orbitals, thus promoting the adsorption and catalytic conversion of LiPSs. While the concave porous carbon not only accommodates the volume change upon the cycling processes but also physically confines and exposes active sites for accelerated sulfur redox reactions. As a result, the resultant HEMN/N-CPC composites-based sulfur cathode can deliver a high specific capacity of 1274 mAh g-1 at 0.2 C and a low capacity decay rate of 0.044% after 1000 cycles at 1 C. Moreover, upon sulfur loading of 5.0 mg cm-2, the areal capacity of 5.0 mAh cm-2 can still be achieved. The present work may provide a new avenue for the design of high-performance cathodes in Li-S batteries.
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The most crucial task of petroleum geology is to explore oil and gas reservoirs in the deep underground. As one of the analysis techniques in petroleum geological research, rock thin section identification method includes particle segmentation, which is one of the key steps. A conventional sandstone thin section image typically contains hundreds of mineral particles with blurred boundaries and complex microstructures inside the particles. Moreover, the complex lithology and low porosity of tight sandstone make traditional image segmentation methods unsuitable for solving the complex thin section segmentation problems. This paper combines petrology and image processing technologies. First, polarised sequence images are aligned, and then the images are transformed to the HSV colour space to extract pores. Second, particles are extracted according to their extinction characteristics. Last, a concavity and corner detection matching method is used to process the extracted particles, thereby completing the segmentation of sandstone thin section images. The experimental results show that our proposed method can more accurately fit the boundaries of mineral particles in sandstone images than existing image segmentation methods. Additionally, when applied in actual production scenarios, our method exhibits excellent performance, greatly improving thin section identification efficiency and significantly assisting experts in identification.
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Investigating the formation and transformation mechanisms of spiral-concave crystals holds significant potential for advancing innovative material design and comprehension. We examined the kinetics-controlled nucleation and growth mechanisms of Prussian Blue crystals with spiral concave structures, and constructed a detailed crystal growth phase diagram. The spiral-concave hexacyanoferrate (SC-HCF) crystals, characterized by high-density surface steps and a low stress-strain architecture, exhibit enhanced activity due to their facile interaction with reactants. Notably, the coordination environment of SC-HCF can be precisely modulated by the introduction of diverse metals. Utilizing X-ray absorption fine structure spectroscopy and in-situ ultraviolet-visible spectroscopy, we elucidated the formation mechanism of SC-HCF to Co-HCF facilitated by oriented adsorption-ion exchange (OA-IE) process. Both experimental data, and density functional theory confirm that Co-HCF possesses an optimized energy band structure, capable of adjusting the local electronic environment and enhancing the performance of the oxygen evolution reaction. This work not only elucidates the formation mechanism and coordination regulation for rich steps HCF, but also offers a novel perspective for constructing nanocrystals with intricate spiral-concave structures.
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Three-dimensional (3D) structures constructed via coordination-driven self-assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self-assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self-coordination ligands, herein the design and synthesis of two meta-modified terpyridyl ligands with selective self-complementary coordination moiety are reported and their capability to assemble into two hourglass-shaped nanocages SA and SB is demonstrated. Within these 3D structures, the meta-modified terpyridyl unit preferably coordinates with itself to serve as concave part. By changing the arm length of the ligands, hexamer (SA) and tetramer (SB) are obtained respectively. In-depth studies on the assembly mechanism of SA and SB indicate that the dimers could be formed first via self-complementary coordination and play crucial roles in controlling the final structures. Moreover, both SA and SB can go through hierarchical self-assemblies in solution as well as on solid-liquid interface, which are characterized by transmission electron microscope (TEM) and scanning tunneling microscopy (STM). It is further demonstrated that various higher-order assembly structures can be achieved by tuning the environmental conditions.
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Surface engineering offers opportunities for the design and synthesis of Pt-based alloyed electrocatalysts with high mass activity and resistance to CO poisoning, which is of great significance for methanol electrooxidation. Surface curvature regulation may endow electrocatalysts with enhanced atomic utilization and abundance of unsaturated atoms; however, a reliable synthetic route for controlled construction of tailorable curved surface is still lacking. Here, a colloidal-chemical method to synthesize two types of PtCu branched-structured electrocatalysts, where the concave curvature can be customized is reported. These studies show that, among various synthesis parameters, the concentration of CuCl2 ·2H2 O precursor is the key factor in manipulating the reaction kinetics and determining the concave surface curvature. Significantly, PtCu branched nanocrystals with long and sharp arms (PtCu BNCs-L), featuring a high concave surface curvature, exhibit remarkable activity and stability toward MOR, which is mainly attributed to advanced features of a highly concave surface and the synergistically bifunctional effect from introduced oxophilic Cu metal. In situ Raman spectroscopy and CO stripping test demonstrates weakened CO adsorption and accelerated CO removal on PtCu BNCs-L. This work highlights the importance of surface curvature, opening up an appealing route for the design and synthesis of advanced electrocatalysts with well-defined surface configurations.
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CABs (Concave Actin Bundles) are oriented against the scaffold transversally in a manner different from traditional longitudinal F-actin bundles. CABs are present in a specific area, and do not exist in random areas. Biologically, CABs are developed to attach cells to fibers firmly so that CABs are found near cells. Based on this knowledge, we closely examined 3D confocal microcopy images containing fiber scaffolds, actin, and cells. Then, we assumed that the areas containing high values of compactness of fiber, compactness of actin, and density of cells would have many numbers of CABs.In this research, we wanted to prove this assumption. We first incorporated a two-point correlation function to define a measure of compactness. Then, we used the Bayes' theorem to prove the above assumption. As the assumption, our results verified that CABs exist in an area of high compactness of a fiber network, high compactness of actin distribution, and high density of cells. Thus, we concluded that CABs are developed to attach cells to a fibrillar scaffold firmly. This finding may be further verified mathematically in future studies.
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Citoesqueleto de Actina , Actinas , Teorema de Bayes , Citoesqueleto , ConhecimentoRESUMO
We propose a unified framework for likelihood-based regression modeling when the response variable has finite support. Our work is motivated by the fact that, in practice, observed data are discrete and bounded. The proposed methods assume a model which includes models previously considered for interval-censored variables with log-concave distributions as special cases. The resulting log-likelihood is concave, which we use to establish asymptotic normality of its maximizer as the number of observations n tends to infinity with the number of parameters d fixed, and rates of convergence of L1 -regularized estimators when the true parameter vector is sparse and d and n both tend to infinity with log ( d ) / n â 0 $\log (d) / n \rightarrow 0$ . We consider an inexact proximal Newton algorithm for computing estimates and give theoretical guarantees for its convergence. The range of possible applications is wide, including but not limited to survival analysis in discrete time, the modeling of outcomes on scored surveys and questionnaires, and, more generally, interval-censored regression. The applicability and usefulness of the proposed methods are illustrated in simulations and data examples.
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Algoritmos , Funções Verossimilhança , Análise de Regressão , Simulação por Computador , Análise de SobrevidaRESUMO
The entire shellfish farming sector is negatively affected by heat waves. Predictive models show that while heat waves are not predicted to exceed 28 °C in the northern Adriatic Sea over the coming decades, their duration will increase to periods of up to 30 days. Knowledge regarding the effects of heat waves on bivalves at physiological and molecular level is still limited. This study attempted to simulate what will happen in the future in Pacific oysters exposed to prolonged heat waves, assessing morphometric and physiological indices, and investigating the expression level of a number of genes, including the chaperone heat shock proteins HSP70, HSP72 and HSP90, and the factor P53. A state of stress in the heat wave-exposed animals was found, with loss of body weight and energy resources: despite showing a higher clearance rate, these animals were unable to absorb the nutrients required to maintain homeostasis, as well as demonstrating an alteration in hemolymphatic AST activity, total calcium and magnesium concentration. mRNA levels of all examined genes increased in response to thermal stress, with long-term overexpression, activating cell stress defense mechanisms and modulating the cycle cell. The results of this study indicate that heat waves affect oyster welfare, with consequences for the productivity of the sector due to the lack of salable products.
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Crassostrea , Animais , Crassostrea/metabolismo , Proteínas de Choque Térmico/genética , Proteínas de Choque Térmico/metabolismo , Proteínas de Choque Térmico HSP70/metabolismo , Proteínas de Choque Térmico HSP90/genética , RNA Mensageiro/metabolismoRESUMO
PURPOSE: To identify the clinical and radiological outcomes in the coronal and sagittal planes after treatment of congenital complex lumbosacral hemivertebrae (LSHV) with or without posterior concave reconstruction. METHODS: We retrospectively reviewed a consecutive series of patients with congenital LSHV deformities treated by posterior-only hemivertebra resection. The minimum follow-up was 2 years. The patients were divided into a concave-cage group and a non-cage group. The radiographic and clinical results were compared between the two groups. RESULTS: Forty patients were categorized into the cage group (n = 14) and non-cage group (n = 26). At the end of the propensity score matching analysis, 14 patients from the cage group were matched to 14 patients in the non-cage group. The lumbosacral curve and thoracolumbar/lumbar curve improved significantly in both groups at the final postoperative follow-up (P < 0.001), and the lumbosacral curve at the final follow-up was remarkably lower in the cage than non-cage group. The correction rates of the lumbosacral curve and thoracolumbar/lumbar curve were significantly higher in the cage than non-cage group. The lower lumbar lordosis improved significantly in both groups at the final postoperative follow-up (P < 0.05), and the lower lumbar lordosis at the final follow-up and its correction were remarkably higher in the cage than non-cage group (both P < 0.05). CONCLUSIONS: Posterior column reconstruction with insertion of a concave cage may achieve a higher correction rate of large lower lumbar lordosis and lumbosacral coronal deformity, attain better sagittal balance, and have fewer complications related to implant failure than posterior-only hemivertebra resection in patients with congenital LSHV.
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Combat soldiers are currently faced with using a hearing-protection device (HPD) at the cost of adequately detecting critical signals impacting mission success. The current study tested the performance of the Perforated-Concave-Earplug (pCEP), a proof-of-concept passive HPD consisting of a concave bowl-like rigid structure attached to a commercial roll-down earplug, designed to improve sound localization with minimal compromising of noise attenuation. Primarily intended for combat/military training settings, our aim was an evaluation of localization of relevant sound sources (single/multiple gunfire, continuous noise, spoken word) compared to 3M™-Combat-Arms™4.1 earplugs in open-mode and 3M™-E-A-R™-Classic™ earplugs. Ninety normal-hearing participants, aged 20-35 years, were asked to localize stimuli delivered from monitors evenly distributed around them in no-HPD and with-HPD conditions. The results showed (1) localization abilities worsened using HPDs; (2) the spoken word was localized less accurately than other stimuli; (3) mean root mean square errors (RMSEs) were largest for stimuli emanating from rear monitors; and (4) localization abilities corresponded to HPD attenuation levels (largest attenuation and mean RMSE: 3M™-E-A-R™-Classic™; smallest attenuation and mean RMSE: 3M™-Combat-Arms™4.1; pCEP was mid-range on both). These findings suggest that the pCEP may benefit in military settings by providing improved sound localization relative to 3M™ E-A-R™-Classic™ and higher attenuation relative to 3M™-Combat Arms™-4.1, recommending its use in noisy environments.
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Militares , Localização de Som , Humanos , Dispositivos de Proteção das Orelhas , SomRESUMO
Map space composition is the first step in ship route planning. In this study, a map modeling method for path planning is proposed. This method incorporates the safety margin based on the theory of geographic space existing in coastal waters, maneuvering space according to ship characteristics, and the psychological buffer space of a ship navigator. First, the obstacle area was segmented using the binary method-a segmentation method-based on the international standard electronic chart image. Next, the margin space was incorporated through the morphological algorithm for the obstacle area. Finally, to minimize the space lost during the route search, the boundary simplification of the obstacle area was performed through the concave hull method. The experimental results of the proposed method resulted in a map that minimized the area lost due to obstacles. In addition, it was found that the distance and path-finding time were reduced compared to the conventional convex hull method. The study shows that the map modeling method is feasible, and that it can be applied to path planning.
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Currently, phased arrays are increasingly used in ultrasonic nondestructive testing. One of the most important parameters of ultrasonic nondestructive testing with the application of phased arrays is the angular resolution. This paper presents the results of studies of the angular resolution of concave and convex acoustic arrays in ultrasonic testing with the application of the total focusing method. Computer modeling of concave and convex acoustic arrays consisting of 16, 32 and 64 elements with distances between elements of 0.5 and 1 mm and arc radii of 30 and 60 mm have been performed. The results obtained by computer modeling were confirmed via in situ experiments.
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Ultrassom , Simulação por ComputadorRESUMO
Practitioners of current data analysis are regularly confronted with the situation where the heavy-tailed skewed response is related to both multiple functional predictors and high-dimensional scalar covariates. We propose a new class of partially functional penalized convolution-type smoothed quantile regression to characterize the conditional quantile level between a scalar response and predictors of both functional and scalar types. The new approach overcomes the lack of smoothness and severe convexity of the standard quantile empirical loss, considerably improving the computing efficiency of partially functional quantile regression. We investigate a folded concave penalized estimator for simultaneous variable selection and estimation by the modified local adaptive majorize-minimization (LAMM) algorithm. The functional predictors can be dense or sparse and are approximated by the principal component basis. Under mild conditions, the consistency and oracle properties of the resulting estimators are established. Simulation studies demonstrate a competitive performance against the partially functional standard penalized quantile regression. A real application using Alzheimer's Disease Neuroimaging Initiative data is utilized to illustrate the practicality of the proposed model.
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Algoritmos , Doença de Alzheimer , Humanos , Modelos Lineares , Simulação por Computador , Análise de DadosRESUMO
INTRODUCTION: Acute angle between dome and ala causes alar concavity/pinch deformity. Breathing problems may accompany pinching. Here, pinch deformities were classified according to their severity and treatment modalities discussed. MATERIALS AND METHODS: Rhinoplasty patients with pinch deformities were included in study. Pinching without external nasal valve blockage (ENVB) was classified mild, pinching with ENVB was classified moderate, and extreme pinching and ENVB were classified severe deformity. In mild deformity, cephalic resection of ala was performed or cephalic resection was combined with onlay graft over ala. In moderate deformity, cephalic part was bent and sutured over lower ala. In severe deformity, cephalic part was bent, and lateral strut graft was inserted between lower and cephalic ala. In pinch deformities combined with hypertrophic lower lateral cartilage (LLC), medial crural overlay preceded above-mentioned treatment modalities. RESULTS: Thirty-eight patients (22 female, 16 male) with pinch deformities underwent rhinoplasty between January 2017 and December 2022. Mean age was 27 years. Mean follow-up was 32 months. Fifteen patients had mild deformities. Cephalic resection was enough in four patients. Camouflage grafts were settled over ala in eleven patients. Twenty patients had moderate deformities; cephalic ala was bent over lower part and sutured. Two patients had severe deformities; lateral strut graft was settled between lower and bent cephalic alar parts. One patient had LLC hypertrophy/pinch deformity. LLC hypertrophy was corrected by medial crural overlay, and concavity was corrected with cephalic resection. Satisfactory shape, better valve passage obtained in all cases. CONCLUSION: Pinch deformity could be classified according to its severity and appropriate treatment options could be determined for each class. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors https://www.springer.com/journal/00266 .
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Obstrução Nasal , Rinoplastia , Humanos , Masculino , Feminino , Adulto , Septo Nasal/cirurgia , Resultado do Tratamento , Estudos Retrospectivos , Estética , Cartilagens Nasais/cirurgia , Rinoplastia/efeitos adversos , Obstrução Nasal/cirurgia , Hipertrofia/cirurgia , Nariz/cirurgiaRESUMO
Knowledge of the parameters of the human spine is essential in designing ergonomic furniture. The purpose of this study was to evaluate spinal alignment in adolescents of various ages. The lengths, curvatures, and concave-convex spacings of the spine were investigated in 268 participants aged 9-18 years. Ten ages were classified, and the rate of increase of parameters was calculated for each age and age group. The results showed that spinal parameters, except for cervical lordosis, increased with age. Adolescents were classified as 9-10, 11-12, 13-15, and 16-18 years old. A rapid increment of lengths and concave-convex spacings occurred at ages 13-15, while that of curvatures occurred at ages 16-18. Spinal parameters differed significantly among the age groups (p < 0.05). Concave-convex spacings reflected differences in the spine more clearly than the other parameters. This study suggests the necessity of designing spine-related furniture based on spinal parameters, thus providing adaptive support for the adolescent spine, particularly the lumbar spine. Practitioner summary: This study examined spinal lengths, curvatures, and concave-convex spacings in adolescents aged 9-8 years and then divided them into four age groups. Concave-convex spacings effectively reflected spinal differences between age groups, particularly the lumbar spine. These results can inform the ergonomic design of spine-related furniture.HIGHLIGHTSSpinal parameters increased progressively between 9 and 18 years. Regression analysis showed good linear correlations between TK, LL, SK, TS, and LS with age.Age classification of adolescents was Group I (9-10 years), Group II (11-12 years), Group III (13-15 years), and Group IV (16-18 years). The rapid increment of lengths and concave-convex spacings were in Group III while that of curvatures were in Group IV.Concave-convex spacings were vital parameters to evaluate the global balance of the spine.The lumbar spine is an essential segment for characterizing spinal alignment.
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Lordose , Escoliose , Adolescente , Humanos , Decoração de Interiores e Mobiliário , Coluna Vertebral , Vértebras LombaresRESUMO
It is well known that the traditional Jensen inequality is proved by lower bounding the given convex function, f(x), by the tangential affine function that passes through the point (E{X},f(E{X})), where E{X} is the expectation of the random variable X. While this tangential affine function yields the tightest lower bound among all lower bounds induced by affine functions that are tangential to f, it turns out that when the function f is just part of a more complicated expression whose expectation is to be bounded, the tightest lower bound might belong to a tangential affine function that passes through a point different than (E{X},f(E{X})). In this paper, we take advantage of this observation by optimizing the point of tangency with regard to the specific given expression in a variety of cases and thereby derive several families of inequalities, henceforth referred to as "Jensen-like" inequalities, which are new to the best knowledge of the author. The degree of tightness and the potential usefulness of these inequalities is demonstrated in several application examples related to information theory.
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We propose a novel two-stage procedure for change point detection and parameter estimation in a multi-threshold proportional hazards model. In the first stage, we estimate the number of thresholds by formulating the threshold detection problem as a variable selection problem and applying the penalized partial likelihood approach. In the second stage, the change point locations are refined by a grid search and the standard inference for segment regression can then follow. The proposed model and estimation procedure could lend support to subgroup identification and personalized treatment recommendation in medical research. We establish the consistency of the threshold estimators and regression coefficient estimators under technical conditions. The finite sample performance of the method is demonstrated via simulation studies and two cancer data examples.
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Neoplasias , Projetos de Pesquisa , Humanos , Modelos de Riscos Proporcionais , Funções Verossimilhança , Simulação por Computador , Neoplasias/terapiaRESUMO
BACKGROUND: Schizophrenia is a chronic, severe, and debilitating mental disorder always considered one of the recurrent psychiatric diseases. This study aimed to use penalized count regression models to determine factors associated with the number of rehospitalizations of schizophrenia disorder. METHODS: This retrospective cohort study was performed on 413 schizophrenic patients who had been referred to the Sina (Farshchian) Educational and Medical Center in Hamadan, Iran, between March 2011 and March 2019. The penalized count regression models were fitted using R.3.5.2. RESULTS: About 73% of the patients were male. The mean (SD) of age and the number of rehospitalizations were 36.16 (11.18) years and 1.21 (2.18), respectively. According to the results, longer duration of illness (P < 0.001), having a positive family history of psychiatric illness (P = 0.017), having at least three children (P = 0.013), unemployment, disability, and retirement (P = 0.025), residence in other Hamadan province townships (P = 0.003) and having a history of arrest/prison (P = 0.022) were significantly associated with an increase in the number of rehospitalizations. CONCLUSION: To reduce the number of rehospitalizations among schizophrenic patients, it is recommended to provide special medical services for patients who do not have access to specialized medical centers and to create the necessary infrastructure for the employment of patients.
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Esquizofrenia , Criança , Feminino , Humanos , Irã (Geográfico) , Masculino , Estudos Retrospectivos , Esquizofrenia/terapia , Fatores de TempoRESUMO
BACKGROUND: The electrocardiographic diagnosis of acute myocardial infarction (AMI) in the setting of cardiac pacing is often challenging. The original Sgarbossa criteria proposed in 1996 were demonstrated to be valid for diagnosis of AMI in both ventricular paced rhythm and left bundle branch block. To improve accuracy, the modified Sgarbossa criteria (MSC) were proposed. CASE PRESENTATION: We presented a case of electrocardiographic diagnosis of AMI in a pacemaker patient. The Electrocardiogram (ECG) was false negative by using the original Sgarbossa criteria, whereas true positive by the MSC at a ratio of - 0.20. CONCLUSIONS: The application of MSC using an appropriate ratio (- 0.20 or - 0.25) may facilitate a timely diagnosis of AMI. Physicians should carefully choose the appropriate cutoff in a case-by-case basis.