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Multinuclear, self-assembled lanthanide complexes present clear opportunities as sensors and imaging agents. Despite the widely acknowledged potential of this class of supramolecule, synthetic and characterization challenges continue to limit systematic studies into their self-assembly restricting the number and variety of lanthanide architectures reported relative to their transition metal counterparts. Here we present the first study evaluating the effect of ligand backbone symmetry on multinuclear lanthanide complex self-assembly. Replacement of a symmetric ethylene linker with an unsymmetric amide at the center of a homoditopic ligand governs formation of an unusual Ln6 L6 complex with coordinatively unsaturated metal centers. The choice of triflate as a counterion, and the effect of ionic radii are shown to be critical for formation of the Ln6 L6 complex. The atypical Ln6 L6 architecture is characterized using a combination of mass spectrometry, luminescence, DOSY NMR and EPR spectroscopy measurements. Luminescence experiments support clear differences between comparable Eu6 L6 and Eu2 L3 complexes, with relatively short luminescent lifetimes and low quantum yields observed for the Eu6 L6 structure indicative of non-radiative decay processes. Synthesis of the Gd6 L6 analogue allows three distinct Gdâ¯Gd distance measurements to be extracted using homo-RIDME EPR experiments.
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In order to effectively balance enforced guidance/regulation during a pandemic and limit infection transmission, with the necessity for public transportation services to remain safe and operational, it is imperative to understand and monitor environmental conditions and typical behavioural patterns within such spaces. Social distancing ability on public transport as well as the use of advanced computer vision techniques to accurately measure this are explored in this paper. A low-cost depth-sensing system is deployed on a public bus as a means to approximate social distancing measures and study passenger habits in relation to social distancing. The results indicate that social distancing on this form of public transport is unlikely for an individual beyond a 28% occupancy threshold, with an 89% chance of being within 1-2 m from at least one other passenger and a 57% chance of being within less than one metre from another passenger at any one point in time. Passenger preference for seating is also analysed, which clearly demonstrates that for typical passengers, ease of access and comfort, as well as seats having a view, are preferred over maximising social-distancing measures. With a highly detailed and comprehensive set of acquired data and accurate measurement capability, the employed equipment and processing methodology also prove to be a robust approach for the application.
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Distanciamiento Físico , Transportes , Transportes/métodos , Pandemias/prevención & controlRESUMEN
Stimuli-responsive polymers are capable of reacting to an external trigger. We report self-regulated, enzymatically active, and pH-responsive hydrogels that show dynamic behavior without an external trigger. This is enabled by a feedback loop between the enzymatic conversion of glucose into gluconic acid and the pH-induced volume phase transition that leads to a modulation in glucose permeability. The synthesized hydrogel spheres combine all required properties for sustained oscillation including enzymatic activity, switchable reactivity, hysteresis in volume phase transition and feedback between the reaction and permeation. A simple model of the system identified possible operating points where sustained oscillations are possible. Experiments at these operating points revealed that the system is able to perform a self-regulated oscillation cycle under a constant nutrient supply. A sensitivity analysis showed that the system is especially sensitive around the point of oscillation, so that precise control of the process parameters is essential to achieve sustained oscillations.
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Glucosa , Hidrogeles , Concentración de Iones de Hidrógeno , Transición de FaseRESUMEN
Traffic cameras are a widely available source of open data that offer tremendous value to public authorities by providing real-time statistics to understand and monitor the activity levels of local populations and their responses to policy interventions such as those seen during the COrona VIrus Disease 2019 (COVID-19) pandemic. This paper presents an end-to-end solution based on the Google Cloud Platform with scalable processing capability to deal with large volumes of traffic camera data across the UK in a cost-efficient manner. It describes a deep learning pipeline to detect pedestrians and vehicles and to generate mobility statistics from these. It includes novel methods for data cleaning and post-processing using a Structure SImilarity Measure (SSIM)-based static mask that improves reliability and accuracy in classifying people and vehicles from traffic camera images. The solution resulted in statistics describing trends in the 'busyness' of various towns and cities in the UK. We validated time series against Automatic Number Plate Recognition (ANPR) cameras across North East England, showing a close correlation between our statistical output and the ANPR source. Trends were also favorably compared against traffic flow statistics from the UK's Department of Transport. The results of this work have been adopted as an experimental faster indicator of the impact of COVID-19 on the UK economy and society by the Office for National Statistics (ONS).
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COVID-19 , Peatones , Accidentes de Tránsito/prevención & control , Ciudades , Humanos , Reproducibilidad de los Resultados , SARS-CoV-2 , SeguridadRESUMEN
Metal-organic frameworks (MOFs) are suitable enzyme immobilization matrices. Reported here is the in situ biomineralization of glucose oxidase (GOD) into MOF crystals (ZIF-8) by interfacial crystallization. This method is effective for the selective coating of porous polyethersulfone microfiltration hollow fibers on the shell side in a straightforward one-step process. MOF layers with a thickness of 8â µm were synthesized, and fluorescence microscopy and a colorimetric protein assay revealed the successful inclusion of GOD into the ZIF-8 layer with an enzyme concentration of 29±3â µg cm-2 . Enzymatic activity tests revealed that 50 % of the enzyme activity is preserved. Continuous enzymatic reactions, by the permeation of ß-d-glucose through the GOD@ZIF-8 membranes, showed a 50 % increased activity compared to batch experiments, emphasizing the importance of the convective transport of educts and products to and from the enzymatic active centers.
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Glucosa Oxidasa/química , Membranas Artificiales , Estructuras Metalorgánicas/química , Catálisis , Colorimetría , Microscopía Electrónica de Rastreo , Microscopía FluorescenteRESUMEN
The meniscal tissue is a layered material with varying properties influenced by collagen content and arrangement. Understanding the relationship between structure and properties is crucial for disease management, treatment development, and biomaterial design. The internal layer of the meniscus is softer and more deformable than the outer layers, thanks to interconnected collagen channels that guide fluid flow. To investigate these relationships, we propose an integrated approach that combines Computational Fluid Dynamics (CFD) with Image Analysis (CFD-IA). We analyze fluid flow in the internal architecture of the human meniscus across a range of inlet velocities (0.1 mm/s to 1.6 m/s) using high-resolution 3D micro-computed tomography scans. Statistical correlations are observed between architectural parameters (tortuosity, connectivity, porosity, pore size) and fluid flow parameters (Re number distribution, permeability). Some channels exhibit Re values of 1400 at an inlet velocity of 1.6 m/s, and a transition from Darcy's regime to a non-Darcian regime occurs around an inlet velocity of 0.02 m/s. Location-dependent permeability ranges from 20-32 Darcy. Regression modelling reveals a strong correlation between fluid velocity and tortuosity at high inlet velocities, as well as with channel diameter at low inlet velocities. At higher inlet velocities, flow paths deviate more from the preferential direction, resulting in a decrease in the concentration parameter by an average of 0.4. This research provides valuable insights into the fluid flow behaviour within the meniscus and its structural influences. 3D models and image stack are available to download at https://doi.org/10.5281/zenodo.10401592. STATEMENT OF SIGNIFICANCE: The meniscus is a highly porous soft tissue with remarkable properties of load transfer and energy absorption. We give insight on the mechanism of energy absorption from high resolution uCT scans, never presented before, and a new method which combine CFD and image. The structure is similar to a sandwich structure with a stiff outside layer and a soft internal layer made of collagen channels oriented in a preferential direction guiding the fluid flow, enabling it to accommodate deformation and dissipate energy, making it a potentially optimized damping system. We investigate architectural/ fluid flow parameters- fluid regimes relationship, which is of interest of the readers working on designing suitable biomimetic systems that can be adopted for replacement.
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Hidrodinámica , Menisco , Humanos , Simulación por Computador , Microtomografía por Rayos X , Menisco/diagnóstico por imagen , ColágenoRESUMEN
In cases of euthanasia, determinations of guilt may be influenced by legal and extra-legal factors. This study explores the role that nullification instructions play in juror decision making. A defendant may be viewed as less culpable if the act was done out of mercy and jury nullification may occur as a result. We anticipated that these determinations may be influenced by the manner of death and the relational distance between the defendant and the decedent. It is unknown how euthanasia is viewed when it is performed by a physician compared to a family member or friend. To answer these questions, participants acted as mock jurors in a euthanasia case. The descriptions of the case varied by the presence of nullification instructions, the manner of death, and the defendant's relationship to the decedent. The results revealed significant effects of method of euthanasia and the type of defendant on juror verdicts. Jurors were most likely to acquit in a case that provided nullification instructions and involved a spouse using lethal injection for euthanasia. This finding suggests that different circumstances of a euthanasia case will affect jurors' propensity to focus on personal sympathies and interpretations. Limitations and future directions are discussed.
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Toma de Decisiones , Eutanasia , Humanos , Emociones , Culpa , Derecho PenalRESUMEN
The Miranda warning was drafted in order to inform people of their rights upon arrest in an easy to understand manner. However, to understand the warning a person needs a high school level reading comprehension (which is above the level of most offenders). Among these offenders, deaf and hard-of-hearing (DHH) individuals are particularly prone to misinterpreting the Miranda warning due to language barriers with law enforcement and below average English literacy compared to hearing individuals. Two studies were performed. The first compared Miranda warning comprehension between hearing and DHH participants, and it was found that DHH participants showed overall lower comprehension. The second study, consisting only of DHH participants, compared the effectiveness of four different presentations of the Miranda warning: signed in American Sign Language (ASL), signed in Signed Exact English (SEE), oral presentation, and written presentation. The written presentation demonstrated the lowest comprehension scores while the other three methods showed no significant difference in comprehension. The results suggest that the Miranda warning is best administered to DHH individuals with the assistance of a certified sign language interpreter. Limitations of the sample and directions for future research are discussed.
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Aptitud , Comprensión , Humanos , Lengua de Signos , Escritura , AudiciónAsunto(s)
Lesión Renal Aguda/complicaciones , Anuria/complicaciones , Cálculos Ureterales/complicaciones , Lesión Renal Aguda/diagnóstico , Lesión Renal Aguda/diagnóstico por imagen , Adulto , Anuria/diagnóstico por imagen , Humanos , Masculino , Tomografía Computarizada por Rayos X , Cálculos Ureterales/diagnóstico , Cálculos Ureterales/diagnóstico por imagenRESUMEN
An osteochondral lesion of the talus (OLT) is an idiopathic acquired lesion of the subchondral bone that can lead to debilitating sequelae. The causes of OLT's are still debatable, however, most agree that the etiology is repetitive microtrauma associated with vascular impairment. OLTs are most commonly described in the medial portion of the talus, while lateral involvement is less frequent. If not properly recognized and treated, an OLT may lead to numerous secondary conditions including premature osteoarthritis and functional limitations of the ankle joint. Multiple surgical and non-surgical treatment modalities have been described with varying results. Treatments are usually guided by the patients age, onset of symptoms, severity, and the disease stage according to the Berndt and Harty classification. Recent literature recommends curettage, drilling, or microfracture techniques for lesions which are no larger than 15mm in diameter and no deeper than 7mm. On the other hand, for large lesions or lesions that failed from primary bone marrow stimulation, surgery should be considered for autologous chondrocyte implantation (ACI), osteochondral autograft transplantation (OATs or mosaicplasty), or osteochondral allograft transplantation [1]. This case study examines surgical treatment of an extensive OLT in a 53 year old man who suffered with continuous ankle pain for over 10 years, misdiagnosed as ankle joint arthritis. Level of clinical evidence: Level of evidence 4.
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Cartílago Articular , Procedimientos Ortopédicos , Astrágalo , Aloinjertos , Articulación del Tobillo/cirugía , Trasplante Óseo , Cartílago Articular/cirugía , Humanos , Masculino , Persona de Mediana Edad , Astrágalo/cirugía , Trasplante Autólogo , Resultado del TratamientoRESUMEN
The electrochemical synthesis of hydrogen peroxide (H2O2) using the oxygen reduction reaction (ORR) requires highly catalytic active, selective, and stable electrode materials to realize a green and efficient process. The present publication shows for the first time the application of a facile one-step bottom-up wet-spinning approach for the continuous fabrication of stable and flexible tubular poly(3,4-ethylene dioxythiophene) (PEDOT : PSS) and PEDOT : PSS/carbon nanotube (CNT) hollow fibers. Additionally, electrochemical experiments reveal the catalytic activity of acid-treated PEDOT : PSS and its composites in the ORR forming hydrogen peroxide for the first time. Under optimized conditions, the composite electrodes with 40â wt % CNT loading could achieve a high production rate of 0.01â mg/min/cm2 and a current efficiency of up to 54 %. In addition to the high production rate, the composite hollow fiber has proven its long-term stability with 95 % current retention after 20â h of hydrogen peroxide production.
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There is a desire in regenerative medicine to create biofunctional materials that can control and direct cell function in a precise manner. One particular stem cell of interest, human mesenchymal stem cells (hMSCs), can function as regulators of the immunogenic response and aid in tissue regeneration and wound repair. Here, a porous hydrogel scaffold assembled from microgel subunits was used to recapitulate part of this immunomodulatory behavior. The scaffolds were used to culture a macrophage cell line, while cytokines were delivered exogenously to polarize the macrophages to either a pro-inflammatory (M1) or alternatively activated (M2a) phenotypes. Using a cytokine array, interleukin 10 (IL-10) was identified as one key anti-inflammatory factor secreted by hMSCs in pro-inflammatory conditions; it was elevated (125 ± 25 pg/ml) in pro-inflammatory conditions compared to standard medium (6 ± 10 pg/ml). The ability of hMSC laden scaffolds to reverse the M1 phenotype was then examined, even in the presence of exogenous pro-inflammatory cytokines. Co-culture of M1 and M2 macrophages with hMSCs reduced the secretion of TNFα, a pro-inflammatory cytokine even in the presence of pro-inflammatory stimulatory factors. Next, IL-10 was supplemented in the medium or tethered directly to the microgel subunits; both methods limited the secretion of pro-inflammatory cytokines of encapsulated macrophages even in pro-inflammatory conditions. Cumulatively, these results reveal the potential of biofunctional microgel-based scaffolds as acellular therapies to present anti-inflammatory cytokines and control the immunogenic cascade.
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Primary hyperparathyroidism (pHPT) is a common endocrine disorder that can be cured by parathyroidectomy; patients unsuitable for surgery can be treated with cinacalcet. Availability of surgery may be reduced during COVID-19, and cinacalcet can be used as bridging therapy. In this single-centre retrospective analysis, we investigated the utility and safety of cinacalcet in patients with pHPT receiving cinacalcet between March 2019 and July 2020, including pre-parathyroidectomy bridging. We reviewed and summarised the published literature. Cinacalcet dosages were adjusted by endocrinologists to achieve target calcium < 2.70 mmol/L. Eighty-six patients were identified, with the most achieving target calcium (79.1%) with a mean dose of 39.4 mg/day (±17.1 mg/day) for a median duration of 35 weeks (1-178 weeks). Calcium was normalised in a median time of 5 weeks. The majority of patients commenced cinacalcet of 30 mg/day (78 patients) with the remainder at 60 mg/day (8 patients). Forty-seven patients commencing lower dose cinacalcet (30 mg/day) achieved target calcium without requiring 60 mg/day. Baseline PTH was significantly higher in patients requiring higher doses of cinacalcet. 18.6% of patients reported adverse reactions and 4.7% discontinued cinacalcet. Patients treated with cinacalcet pre-parathyroidectomy required a higher dose and fewer achieved target calcium compared to medical treatment with cinacalcet alone. Post-operative calcium was similar to patients who were not given pre-parathyroidectomy cinacalcet. In summary, cinacalcet at an initial dose of 30 mg/day is safe and useful for achieving target calcium in patients with symptomatic or severe hypercalcaemia in pHPT, including those treated for pre-parathyroidectomy. We propose a PTH threshold of >30 pmol/L to initiate at a higher dose of 60 mg/day.
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Multiplicative reasoning is required in different contexts in mathematics: it is necessary to understand the concept of multipart units, involved in learning place value and measurement, and also to solve multiplication and division problems. Measures of hearing children's multiplicative reasoning at school entry are reliable and specific predictors of their mathematics achievement in school. An analysis of deaf children's informal multiplicative reasoning showed that deaf children under-perform in comparison to the hearing cohorts in their first two years of school. However, a brief training study, which significantly improved their success on these problems, suggested that this may be a performance, rather than a competence difference. Thus, it is possible and desirable to promote deaf children's multiplicative reasoning when they start school so that they are provided with a more solid basis for learning mathematics.
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Cognición , Sordera , Matemática , Solución de Problemas , Niño , Preescolar , Femenino , Humanos , Aprendizaje , MasculinoRESUMEN
BACKGROUND: Colonoscopy is the gold-standard investigation for direct luminal visualization of the large bowel. Studies have shown the efficacy of computed tomography colonography (CTC) is equivalent to colonoscopy in both cancer and polyp detection. METHODS: A retrospective review of patients undergoing CTC from January 2013 to October 2014 was performed. Patient demographics, indication for investigation, computed tomography findings, optical colonoscopy findings and histology results were recorded. RESULTS: Seven hundred and fifty-eight CTC were performed. Three hundred and seventeen patients were male (42%) and 441 (58%) were female. Endoscopy was advised in 209 cases. One hundred and twenty (16%) were deemed suspicious for cancer of whom 96 (80%) had optical colonoscopy. A total of 12 colorectal cancers were detected. Potential polyps were noted in 58 cases (8%). Forty-four patients underwent endoscopy (75%) and 17 polyps confirmed (38%). Two patients had foci of invasive cancer histologically. Significant extracolonic findings were identified in 60%, including five cases of gastric carcinomas. The most common other findings were gallstones and hernias. CONCLUSION: The rate of colorectal cancer detection in this study was 2%. The rate of biopsy proven cancer was 10% following a suspicious colonogram. Endoscopic correlation was not obtained in 20% of cases of radiological suspicion. CTC is as efficacious as optical colonoscopy for colorectal cancer and polyp detection.
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Colonografía Tomográfica Computarizada/métodos , Neoplasias Colorrectales/diagnóstico , Hospitales de Distrito , Hospitales Generales , Adulto , Anciano , Anciano de 80 o más Años , Biopsia , Colonoscopía , Diagnóstico Diferencial , Femenino , Estudios de Seguimiento , Humanos , Masculino , Persona de Mediana Edad , Reproducibilidad de los Resultados , Estudios Retrospectivos , Factores de Tiempo , Adulto JovenRESUMEN
We aimed to investigate oxidative stress biomarkers in a cross-sectional pilot study of 50 participants with sporadic ALS (SALS) compared to 46 control subjects. We measured urinary 8-oxodeoxyguanosine (8-oxodG), urinary 15-F(2t)-isoprostane (IsoP), and plasma protein carbonyl by ELISA methods. We also determined if ELISA measurement of 8-oxodG could be validated against measures from high-pressure liquid chromatography coupled with electrochemical detection, the current standard method. We found that 8-oxodG and IsoP levels adjusted for creatinine were significantly elevated in SALS participants. These differences persisted after age and gender were controlled in regression analyses. These markers are highly and positively correlated with each other. 8-oxodG measured by the two techniques from the same urine sample were positively correlated (p<.0001). Protein carbonyl was not different between SALS participants and controls. In conclusion, using ELISA, we confirmed that certain oxidative stress biomarkers were elevated in SALS participants. ELISA may be reliable and thus useful in epidemiology studies requiring large numbers of samples to determine the significance of increased oxidative stress markers in SALS. Further studies are required.
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Esclerosis Amiotrófica Lateral/epidemiología , Esclerosis Amiotrófica Lateral/metabolismo , Biomarcadores/sangre , Biomarcadores/orina , Estrés Oxidativo , 8-Hidroxi-2'-Desoxicoguanosina , Anciano , Proteínas Sanguíneas/metabolismo , Estudios Transversales , Desoxiguanosina/análogos & derivados , Desoxiguanosina/orina , Dinoprost/análogos & derivados , Dinoprost/orina , Ensayo de Inmunoadsorción Enzimática , Femenino , Humanos , Masculino , Persona de Mediana Edad , Proyectos Piloto , Especies Reactivas de OxígenoRESUMEN
Orbital blowout fractures are nearly always caused by acute trauma. Non-traumatic cases of orbital blowout fractures have only been rarely described. In this case study, we discuss an orbital blowout fracture directly caused by nose blowing. The patient developed unilateral eye swelling and orbital emphysema. It is important for the clinician to investigate all suspected orbital blowout fractures with imaging and full ophthalmological examination regardless of a trauma history. Most cases of orbital emphysema resolve spontaneously, however one must always exclude compression of the central retinal artery. This may present as acute loss of vision and/or ophthalmoplegia.
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Combinación Amoxicilina-Clavulanato de Potasio/uso terapéutico , Barotrauma/complicaciones , Epistaxis/etiología , Nariz/lesiones , Fracturas Orbitales/diagnóstico por imagen , Inhibidores de beta-Lactamasas/uso terapéutico , Adulto , Femenino , Humanos , Fracturas Orbitales/tratamiento farmacológico , Fracturas Orbitales/etiología , Educación del Paciente como Asunto , Derivación y Consulta , Tomografía Computarizada por Rayos X , Resultado del TratamientoRESUMEN
Older patients with advanced illness are presenting more frequently to emergency departments (EDs). These patients have complex needs, which challenge busy EDs tuned to provide emergent, life-sustaining interventions, and rapid dispositions. This article outlines communication skills to assess patient goals so that the ED provider can create a care plan that matches level of medical intervention with patient wishes. Furthermore, this article outlines symptom-based care for the actively dying geriatric patient in the ED, specifically, acute pain, dyspnea, terminal delirium, secretions, dry mouth, fever, and bereavement.
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Enfermedad Crítica , Servicio de Urgencia en Hospital , Cuidados Paliativos/métodos , Cuidado Terminal , Anciano , Enfermedad Crítica/psicología , Enfermedad Crítica/terapia , Humanos , Planificación de Atención al Paciente , Cuidado Terminal/métodos , Cuidado Terminal/organización & administraciónRESUMEN
A 63-year-old man presented with a 4-day history of right sided loin-to-groin pain. Computed tomography imaging revealed a 22 mm by 7 mm volume of contiguous ureteric calculi at the right vesicoureteric junction. Spontaneous steinstrasse was diagnosed with no recent history of extracorporeal shock wave lithotripsy (ESWL) or other urological intervention to the right kidney. Metabolic testing was negative. An initial plan was made for urgent primary ureteroscopy and lithotripsy, however, the patient spontaneously passed 20-25 calculi at home whilst awaiting his operation date. He was reviewed in clinic and his symptoms had resolved. His ureteroscopy was cancelled. This case represents an example of spontaneous steinstrasse with no identified causative factors, a rare occurrence on which little literature is available presenting a management dilemma to the treating clinician. The case described resolved prior to intervention prompting us to suggest that spontaneous steinstrasse can be initially managed conservatively, as in ESWL-associated steinstrasse.
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OBJECTIVE: To analyze patient risk factors and processes of care associated with secondary surgical-site infection (SSI) after coronary artery bypass grafting (CABG). METHODS: Data were collected prospectively between February and October 2010 for consenting adult patients undergoing CABG with saphenous vein graft (SVG) conduits. Patients who developed a deep or superficial SSI of the leg or groin within 65 days of CABG were compared with those who did not develop a secondary SSI. RESULTS: Among 2174 patients identified, 65 (3.0%) developed a secondary SSI. Median time to diagnosis was 16 days (interquartile range 11-29) with the majority (86%) diagnosed after discharge. Gram-positive bacteria were most common. Readmission was more common in patients with a secondary SSI (34% vs 17%, P < .01). After adjustment, an open SVG harvest approach was associated with an increased risk of secondary SSI (adjusted hazard ratio [HR], 2.12; 95% confidence interval [CI], 1.28-3.48). Increased body mass index (adjusted HR, 1.08, 95% CI, 1.04-1.12) and packed red blood cell transfusions (adjusted HR, 1.13; 95% CI, 1.05-1.22) were associated with a greater risk of secondary SSI. Antibiotic type, antibiotic duration, and postoperative hyperglycemia were not associated with risk of secondary SSI. CONCLUSIONS: Secondary SSI after CABG continues to be an important source of morbidity. This serious complication often occurs after discharge and is associated with open SVG harvesting, larger body mass, and blood transfusions. Patients with a secondary SSI have longer lengths of stay and are readmitted more frequently.