Selective Electrochemical Modification and Degradation of Polymers.

We demonstrate that electrochemical-induced decarboxylation enables reliable post-polymerization modification and degradation of polymers. Polymers containing N-(acryloxy)phthalimides were subjected to electrochemical decarboxylation under mild conditions, which led to the formation of transient alkyl radicals. By installing these redox-active units, we systematically modified the pendent groups and chain ends of polyacrylates. This approach enabled the production of poly(ethylene-co-methyl acrylate) and poly(propylene-co-methyl acrylate) copolymers, which are difficult to synthesize by direct polymerization. Spectroscopic and chromatographic techniques reveal these transformations are near-quantitative on several polymer systems. Electrochemical decarboxylation also enables the degradation of all-methacrylate poly(N-(methacryloxy)phthalimide-co-methyl methacrylate) copolymers with a degradation efficiency of >95 %. Chain cleavage is achieved through the decarboxylation of the N-hydroxyphthalimide ester and subsequent ß-scission of the backbone radical. Electrochemistry is thus shown to be a powerful tool in selective polymer transformations and controlled macromolecular degradation.

[Compressive stress in three types of finishing lines with lithium disilicate crowns in permanent teeth: finite element analysis]. / Tensión compresiva en tres tipos de líneas de terminación con coronas de disilicato de litio en dientes permanentes: análisis de elemento finito.

Introduction: In oral rehabilitation, the use of ceramic restorations is widely accepted due to its aesthetic capacity to mimic the naturalness of the dental tissue, provide longevity of the material, and present a greater marginal fit compared to crowns with a metal structure. Termination lines are biological preparations whose function is to minimize the cervical opening of the marginal seal. Consequently, analyzing the behavior of restorative materials under compressive forces decreases the risk of fracture and increases the success of the treatment. Objective: To compare the compressive stresses of lithium disilicate crowns with three different finishing lines. Methodology: In silico study of the simulation of a dental preparation on a lower right first molar with chamfer (0.6 mm), shoulder (0.5 mm) and deep chamfer (0.5 mm) finish lines. Using the SolidWorks®ï¸ version 2017 software, the maximum stresses, minimum stresses, and location of the compressive force were collected on the Megapascal (Mpa) measurement scale. Results: The chamfer type termination line (0.6mm) obtained a lower compressive stress compared to the other two shoulder type termination lines (0.5mm) and deep chamfer (0.5mm). Conclusions: It was shown that the chamfer type finishing line (0.6mm) presented a better force distribution, determining greater reliability in the selection of this finishing line with the use of a lithium disilicate crown in a unitary manner.

Assessing the predictive value of the Risk Analysis Index for short-term outcomes in acute spinal cord injury surgery.

BACKGROUND: Acute traumatic spinal cord injury (tSCI) requires rapid surgical intervention to maximize neurological function. Older patients comprise an increasingly larger proportion of SCI patients annually, necessitating accurate preoperative risk stratification tools. This study utilized a frailty-based preoperative risk stratification score to predict adverse events following non-elective neurosurgical intervention for acute tSCI patients. METHODS: The National Inpatient Sample (NIS) was queried for acute tSCI patients aged ≥18 who underwent spine surgery in 2019-2020. The Risk Analysis Index (RAI) was implemented with crosstabulation, to analyze frailty scores with the following binary outcome measures: overall complications, non-home discharge (NHD), extended length of stay (eLOS) (>75th percentile), and mortality. Area Under the Receiver Operating Characteristic (AUROC) analysis assessed the discriminative threshold of RAI compared to the modified 5-item Frailty Index (mFI-5) for NHD and 30-day mortality. RESULTS: A total of 9995 SCI patients underwent non-elective spine surgery. There were 1525 perioperative complications (15.3%) and 510 (5.1%) mortalities. An increasing RAI score was significantly associated with increasing postoperative mortality rates: RAI 0-20 (1.5%, N.=45), RAI 21-30 (3.4%, N.=110), RAI 31-40 (6.8%, N.=115), and RAI>41 (11.8%, N.=240) (P<0.001). RAI demonstrated superior discrimination compared to the mFI-5 for mortality and NHD with a C-statistic >0.72. CONCLUSIONS: Increasing frailty, as measured by RAI, was a reliable predictor of non-home discharge and 30-day mortality for SCI patients who underwent non-elective spinal surgery and RAI demonstrated superior discrimination compared to the mFI-5 for NHD and mortality.

Electrochemical Postpolymerization Modification and Deconstruction of Macromolecules.

Electrolysis is an emerging approach to polymer postpolymerization modification, deconstruction, and depolymerization. Electrochemical reactions are particularly appealing for macromolecular transformations because of their high selectivity, ability to be externally monitored, and intrinsic scalability. Despite these desirable features and the recent resurgent use of small-molecule electrochemical reactions, the development of macromolecular electrolysis has been limited. Herein, we highlight recent examples of polymer transformations driven by heterogeneous redox chemistry. Throughout our exploration of macromolecular electrolysis, we provide our perspective on opportunities for continued investigation in this nascent field. Specifically, we highlight how targeted reaction development through deeper mechanistic insight will expand the scope of materials that can be (de)constructed with electrochemical methods. As this insight is developed, we expect macromolecular electrolysis to emerge as a high-functioning and complementary tool for macromolecular functionalization and deconstruction.

Electroactive Ionic Polymer of Intrinsic Microporosity for High-Performance Capacitive Energy Storage.

Here, an ionic polymer of intrinsic microporosity (PIM) as a high-functioning supercapacitor electrode without the need for conductive additives or binders is reported. The performance of this material is directly related to its large accessible surface area. By comparing electrochemical performance between a porous viologen PIM and a nonporous viologen polymer, it is revealed that the high energy and power density are both due to the ability of ions to rapidly access the ionic PIM. In 0.1 m H2SO4 electrolyte, a pseudocapacitve energy of 315 F g-1 is observed, whereas in 0.1 m Na2SO4, a capacitive energy density of 250 F g-1 is obtained. In both cases, this capacity is retained over 10 000 charge-discharge cycles, without the need for stabilizing binders or conductive additives even at moderate loadings (5 mg cm-2). This desirable performance is maintained in a prototype symmetric two-electrode capacitor device, which has >99% Coloumbic efficiency and a <10 mF capacity drop over 2000 cycles. These results demonstrate that ionic PIMs function well as standalone supercapacitor electrodes and suggest ionic PIMs may perform well in other electrochemical devices such as sensors, ion-separation membranes, or displays.

Cerebral autoregulation, spreading depolarization, and implications for targeted therapy in brain injury and ischemia.

Cerebral autoregulation is an intrinsic myogenic response of cerebral vasculature that allows for preservation of stable cerebral blood flow levels in response to changing systemic blood pressure. It is effective across a broad range of blood pressure levels through precapillary vasoconstriction and dilation. Autoregulation is difficult to directly measure and methods to indirectly ascertain cerebral autoregulation status inherently require certain assumptions. Patients with impaired cerebral autoregulation may be at risk of brain ischemia. One of the central mechanisms of ischemia in patients with metabolically compromised states is likely the triggering of spreading depolarization (SD) events and ultimately, terminal (or anoxic) depolarization. Cerebral autoregulation and SD are therefore linked when considering the risk of ischemia. In this scoping review, we will discuss the range of methods to measure cerebral autoregulation, their theoretical strengths and weaknesses, and the available clinical evidence to support their utility. We will then discuss the emerging link between impaired cerebral autoregulation and the occurrence of SD events. Such an approach offers the opportunity to better understand an individual patient's physiology and provide targeted treatments.

Baseline Frailty and Discharge to Advanced Care Facilities in Patients Undergoing Lumbar Interbody Fusion for Lumbar Degenerative Disease: A Multicenter Registry Analysis of 7153 Patient Cases Comparing the Risk Analysis Index to the 5-Factor Modified Frailty Index.

OBJECTIVE: To evaluate the impact of frailty, as measured by the 5-factor modified Frailty Index (mFI-5) and the Risk Analysis Index (RAI), on advanced care facility discharge (FD) in patients who underwent lumbar fusion for lumbar degenerative spine disease. METHODS: The American College of Surgeons National Surgical Quality Improvement Program (2012-2020) was queried for adults (≥18 years) undergoing lumbar fusion for lumbar degenerative disease. Descriptive statistics and univariate crosstabulation were used to assess baseline demographics, preoperative comorbidities, and postoperative outcomes. Receiver operating characteristic curve analysis was used to assess the discriminative threshold of the mFI-5 and RAI on FD within this population. RESULTS: The median patient age in this study cohort (N = 7153) was 56 years and FD occurred in 7.3% of cases. Receiver operating characteristic curve analysis demonstrated that both the mFI-5 and the RAI accurately predicted FD (C-statistics: mFI-5: 0.627; RAI: 0.746). DeLong's test found that the RAI had superior discrimination when compared to the mFI-5 (P < 0.0001). CONCLUSIONS: RAI is a reliable predictor of FD in lumbar degenerative disease patients who underwent lumbar interbody fusion and demonstrated superior discrimination compared to the mFI-5. Identification of patients at risk for FD may facilitate more precise risk stratification to enable better preoperative decision-making and help set more realistic expectations of care.

Vacuum-assisted scalp repositioning: a novel temporizing approach to acute sinking skin flap syndrome. Illustrative cases.

BACKGROUND: This report describes the use of a novel approach to address acute sinking skin flap syndrome (SSFS), a postcraniectomy complication arising from brain dysfunction beneath the skull defect. The authors present a case series of two patients, emphasizing the prospective application of an external plaster cast in tandem with a vacuum-assisted closure (VAC) device (wound VAC) to promptly reposition the scalp and relieve brain compression. OBSERVATIONS: Following intervention, one patient showed immediate neurological improvement, with complete resolution of symptoms within hours. Conversely, the second patient developed nonconvulsive status epilepticus. Computed tomography scans postintervention validated the successful scalp repositioning and mass effect resolution in both instances. This temporary approach proved successful in one patient with moderate symptoms, serving as a bridge to cranioplasty. LESSONS: The integration of an external plaster cast and wound VAC offers a cost-effective and prompt solution for patients with acute SSFS pending cranioplasty. Appropriate patient selection and heightened caution for those with severe symptoms should be exercised.

Pathomechanisms and Treatment Implications for Stroke in COVID-19: A Review of the Literature.

Stroke in patients with COVID-19 has received increasing attention throughout the global COVID-19 pandemic, perhaps due to the substantial disability and mortality that can result when the two conditions co-occur. We reviewed the existing literature and found that the proposed pathomechanism underlying COVID-19-associated ischemic stroke is broadly divided into the following three categories: vasculitis, endothelialitis, and endothelial dysfunction; hypercoagulable state; and cardioembolism secondary to cardiac dysfunction. There has been substantial debate as to whether there is a causal link between stroke and COVID-19. However, the distinct phenotype of COVID-19-associated strokes, with multivessel territory infarcts, higher proportion of large vessel occlusions, and cryptogenic stroke mechanism, that emerged in pooled analytic comparisons with non-COVID-19 strokes is compelling. Further, in this article, we review the various treatment approaches that have emerged as they relate to the proposed pathomechanisms. Finally, we briefly cover the logistical challenges, such as delays in treatment, faced by providers and health systems; the innovative approaches utilized, including the role of tele-stroke; and the future directions in COVID-19-associated stroke research and healthcare delivery.