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1.
Article in English | MEDLINE | ID: mdl-38990772

ABSTRACT

A novel zwitterion composed of an imidazolium tethered to an anionic sulfonyl(trifluoromethane sulfonyl)imide group was prepared as an alternative dielectric material to traditional ionic liquids. The zwitterion not only melted below 100 °C but also proved to be nonhygroscopic. High-capacitance organic dielectric materials were obtained by blending this compound with poly(methyl methacrylate) over a range of concentrations and thicknesses. Above a specific temperature and concentration, films exhibit a capacitance nearly equivalent to that of an electrostatic double layer, approximately 10 µF/cm2, regardless of their thickness. Grazing-incidence wide-angle X-ray scattering experiments suggest that the zwitterions adopt a lamellar ordering at their surface above a critical concentration. The observed ordering is correlated with a 1000-fold increase in capacitance. The behavior suggests that the zwitterions exhibit strong electrostatic correlations throughout the film bulk, pointing the way toward a novel class of organic dielectric materials.

2.
J Neurosurg Pediatr ; : 1-9, 2024 Jun 21.
Article in English | MEDLINE | ID: mdl-38905709

ABSTRACT

OBJECTIVE: The aim of this study was to compare clinical and craniometric outcomes of patients treated for hydrocephalus following fetal myelomeningocele repair (fMMR) via a ventriculoperitoneal shunt (VPS) or endoscopic third ventriculostomy with choroid plexus cauterization (ETV/CPC). METHODS: This was a retrospective cohort study of children who were treated for hydrocephalus following fMMR via VPS or ETV with or without CPC (ETV ± CPC) at Vanderbilt between 2012 and 2021. The primary outcomes were treatment failure and time to failure (TTF). Secondary outcomes included changes in hydrocephalus metrics (fronto-occipital horn ratio [FOHR] and head circumference measurements) and healthcare resource utilization (number of hospital admissions, clinic visits, and neuroimaging findings). RESULTS: Among 88 patients who underwent fMMR, 37 (42%) required permanent CSF diversion, of whom 19 received treatment at the authors' institution. Twelve patients underwent ETV ± CPC, and 7 underwent VPS placement at a median corrected age of 23 weeks versus 1 week (p = 0.002). The preoperative median head circumference percentiles and z-scores for patients in the ETV ± CPC cohort were similar to those of the VPS cohort (percentiles: 98.5 vs 94.0, p = 0.064; z-scores: 2.32 vs 1.60, p = 0.111). There was no difference in preoperative median FOHR measurements between the two cohorts (0.57 vs 0.59, p = 0.53). At 6 months postoperatively, the median head circumference percentile and z-score for the ETV ± CPC cohort remained similar between the two cohorts (percentiles: 98.0 vs 67.5, p = 0.315; z-scores: 2.12 vs 0.52, p = 0.307). There was no difference in the change in FOHR (-0.06 vs -0.09, p = 0.37) and change in head circumference percentile (-1.33 vs -28.6, p = 0.058) between the cohorts 6 months after the index CSF diversion procedure. One patient in the ETV ± CPC cohort experienced a seizure and a nonoperative subdural hemorrhage postoperatively; no other complications were observed. Six of the 7 patients in the VPS cohort required shunt revision with a median TTF of 9.8 months while 2 of the 12 ETV ± CPC patients required a repeat ETV at a median of 17.5 months (86% vs 17%, p = 0.013). The median number of hydrocephalus-related hospital readmissions was significantly lower in the ETV ± CPC cohort than in the VPS cohort (0 vs 1, p = 0.006). The ETV ± CPC cohort had fewer CT scans (0 vs 2, p = 0.004) and radiographs (0 vs 2, p < 0.001) than the VPS cohort. CONCLUSIONS: In a single-center cohort, hydrocephalic fMMR patients treated via ETV ± CPC remained shunt free, while a majority of patients receiving an upfront shunt required revision. This is the first study comparing ETV ± CPC with VPS in the fMMR hydrocephalus population. While larger, multicenter studies are needed, these results suggest that ETV/CPC may be a preferred means of CSF diversion following fMMR.

3.
Soft Matter ; 20(22): 4504-4514, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38804153

ABSTRACT

Although discotic dimers commonly feature bulky ether substituents adjacent to the linking group, the impact of these chains on self-assembly remains unclear. A series of dibenzo[a,c]phenazine dimers with alkoxy groups ortho to the linker were prepared and their solution conformational dynamics and liquid crystalline properties examined. The presence of a methoxy substitutent adjacent to the bridging group increased the phase stability, whereas longer chains dramatically decreased clearing temperatures. NMR solution studies indicated that adjacent groups increased the preference of dimers to adopt unfolded conformers. DFT models indicated that the unfolded structures were nonplanar and hence less compatible with columnar ordering, leading to a destabilization of the mesophases.

4.
J Neurosurg Pediatr ; 33(4): 390-397, 2024 Apr 01.
Article in English | MEDLINE | ID: mdl-38306638

ABSTRACT

OBJECTIVE: Most studies regarding sport-related concussion (SRC) focus on high school and collegiate athletes; however, little has been published on children younger than 12 years of age. In a cohort of children aged 8-12 years with SRC, the authors sought to describe demographics, initial presentation, and recovery in this understudied population. METHODS: A retrospective cohort study of children aged 8-12 years who sustained an SRC between November 2017 and April 2022 and were treated at a regional sports concussion center was conducted. Demographic information, injury characteristics, traditional Sport Concussion Assessment Tool 5 (SCAT5) and Child/Parent SCAT5 scores, and outcomes, defined as days to return to learn (RTL), symptom resolution, and return to play (RTP), were reported. Outcomes in boys and girls were compared using effect size analyses given sample size constraints. RESULTS: Forty-seven athletes were included. The mean age was 11.0 ± 0.8 years, and the majority were male (34, 72.3%). A sizable proportion of patients visited an emergency department (19, 40.4%), and many received head imaging (16, 34.0%), mostly via CT (n = 13). The most common sport for boys was football (15, 44.1%), and the most common sports for girls were soccer (4, 30.8%) and cheerleading (4, 30.8%). These athletes reported a variety of symptoms on presentation. It took a mean of 8.8 ± 10.8 days to RTL, 27.3 ± 38.3 days to reach symptom resolution, and 35.4 ± 41.9 days to RTP. When comparing boys versus girls, there appeared to be moderate differences in symptom severity scores (Cohen's d = 0.44 for SCAT5, 0.13 for Child SCAT5, and 0.38 for Parent SCAT5) and minimal differences in recovery (Cohen's d = 0.11 for RTL, n = 35; 0.22 for symptom resolution, n = 22; and 0.12 for RTP, n = 21). CONCLUSIONS: In this cohort of concussed athletes aged 8-12 years, a little less than half of the athletes initially presented to the emergency department, and approximately one-third received acute head imaging. Across all athletes, the mean RTL was slightly more than a week and the mean symptom resolution and RTP were both approximately 1 month; however, much of the cohort is missing recovery outcome measures. This study demonstrated a strong positive correlation between Child SCAT5 and Parent SCAT5 symptom reporting. Future efforts are needed to evaluate differences in clinical presentation and outcomes following SRC between children and older populations.


Subject(s)
Athletic Injuries , Brain Concussion , Soccer , Child , Humans , Male , Female , Athletic Injuries/diagnostic imaging , Athletic Injuries/epidemiology , Retrospective Studies , Neuropsychological Tests , Brain Concussion/diagnostic imaging , Brain Concussion/epidemiology , Athletes , Soccer/injuries
5.
Neurosurgery ; 2024 Feb 15.
Article in English | MEDLINE | ID: mdl-38358270

ABSTRACT

BACKGROUND AND OBJECTIVES: While spinal cord neurapraxia (SCN) is a documented pathology in athletes, guidance for neurosurgeons evaluating these patients is sparse. Therefore, in a cohort of adolescent athletes with SCN, we sought to (1) review their presentation and management and (2) describe outcomes and return-to-play (RTP). METHODS: A single-center, retrospective case series was conducted to examine adolescent athletes diagnosed with SCN from 2017 to 2022. SCN was defined as an episode of bilateral upper and/or lower extremity weakness/numbness after an impact during sport. Collected variables included demographics, presentation, management, outcomes, and RTP. RESULTS: Six patients were included (mean age = 14.5 ± 2.1 years, 100.0% male). Three American football players sustained tackle injuries, 1 ice hockey and 1 basketball player fell and landed on their head/neck, and 1 weight lifter sustained an axial load of weights to his neck. Motor symptoms ranged from quadriplegia to partial weakness. Full symptom resolution was seen in 6/6 patients: in <1 day for 3 patients, 2-3 days for 2 patients, and 1-2 months for 1 patient. All 6/6 patients received computed tomography of head/cervical spine and MRI of cervical spine, half of whom received computed tomography and MRI of thoracic/lumbar spine. No patient had congenital stenosis or abnormal T2 signal on MRI. Specific RTP recommendations varied. All 6 patients/parents were contacted at a mean of 16.6 ± 2.6 months from the injury. All patients returned to play at a mean of 5.7 ± 3.3 months. All 6 patients returned to their previous sports. Across all patients, no recurrence or neurological sequelae was endorsed in the follow-up period. CONCLUSION: Six athletes with SCN with no imaging abnormalities and full symptom resolution were able to RTP to their previous sport without future consequence. Symptom duration may not be clinically useful in determining the feasibility of RTP. Follow-up studies are warranted in this patient cohort to standardize RTP recommendations.

6.
Dalton Trans ; 53(3): 938-948, 2024 Jan 16.
Article in English | MEDLINE | ID: mdl-38108471

ABSTRACT

A series of [PcMnL2]SbF6 complexes (Pc = phthalocyanine) was synthesized and structurally characterized by stripping the chloride from PcMnCl with AgSbF6 in o-dichlorobenzene and adding a range of donor ligands (L = THF, pyridine, p-dimethylaminopyridine (DMAP), Ph3PO, N-methylimidazole (MeIm), MeCN) to the resulting solution. Addition of or exposure to water where L = heterocyclic amines yielded µ-oxo complexes of the form [PcMnL]2O, which were structurally characterized for L = DMAP and MeIm. The [PcMnL2]SbF6 complexes have an increased solubility in organic solvents, where the axial ligands inhibit the characteristic ring π-π aggregation of PcM complexes. A variety of colours were observed (blue/green to red/purple), with Q-band absorptions (excluding the µ-oxo species) spanning from 715-761 nm and LMCT-bands from 497-574 nm. The combination of the ligand-induced absorption shifts coupled with their relative intensities in the visible region is responsible for the observed colour range and illustrates that facile ligand exchange is a useful tool in producing materials with a variety of colours from PcMnCl.

7.
Childs Nerv Syst ; 39(11): 3123-3130, 2023 11.
Article in English | MEDLINE | ID: mdl-37099139

ABSTRACT

Open spina bifida (OSB) is a common neural tube defect. Medical and surgical care involves addressing the baseline orthopedic, urologic, and neurological dysfunction as well as the changes or declines that may occur as the patient ages. Given the complexity of this disease, coordinated, multidisciplinary care involving specialists in neurosurgery, orthopedics, urology, rehabilitation and physical medicine, pediatrics, and psychology is necessary to establish and optimize baseline function. Traditionally in the US, pediatric multispecialty spina bifida clinics have provided the patient with a coordinated medical support system. Unfortunately, this coordinated, medical home has been difficult to establish during the transition from pediatric to adult care. Medical professionals must have a strong understanding of OSB to properly manage the disease and detect and prevent associated complications. In this manuscript, we (1) describe the changing needs and challenges of people living with OSB over a lifespan, (2) delineate current practices in the transition of care for people with OSB from childhood to adulthood, and (3) provide recommendations for best practices in navigating the transition process for clinicians who provide care for those afflicted with this most complex congenital abnormality of the nervous system compatible with long term survival.


Subject(s)
Anencephaly , Spina Bifida Cystica , Spinal Dysraphism , Transition to Adult Care , Adult , Humans , Adolescent , Child , Young Adult , Folic Acid , Anencephaly/prevention & control , Food, Fortified , Spinal Dysraphism/therapy
8.
Soft Matter ; 19(15): 2705-2709, 2023 Apr 12.
Article in English | MEDLINE | ID: mdl-36987609

ABSTRACT

A series of discotic dimers were synthesized in an attempt to obtain nematic discotic liquid crystal phases. Although initial target compounds were nonmesogenic, the incorporation of bulky groups adjacent to the ester bridge, in conjunction with peripheral chains of mixed length, were used to promote the formation of an enantiotropic nematic phase.

9.
Crit Care Med ; 51(5): 563-572, 2023 05 01.
Article in English | MEDLINE | ID: mdl-36825892

ABSTRACT

OBJECTIVES: The acute cerebral physiologic effects of ketamine in children have been incompletely described. We assessed the acute effects of ketamine on intracranial pressure (ICP) and cerebral perfusion pressure (CPP) in children with severe traumatic brain injury (TBI). DESIGN: In this retrospective observational study, patients received bolus doses of ketamine for sedation or as a treatment for ICP crisis (ICP > 20 mm Hg for > 5 min). Administration times were synchronized with ICP and CPP recordings at 1-minute intervals logged in an automated database within the electronic health record. ICP and CPP were each averaged in epochs following drug administration and compared with baseline values. Age-based CPP thresholds were subtracted from CPP recordings and compared with baseline values. Trends in ICP and CPP over time were assessed using generalized least squares regression. SETTING: A 30-bed tertiary care children's hospital PICU. PATIENTS: Children with severe TBI who underwent ICP monitoring. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: We analyzed data from 33 patients, ages 1 month to 16 years, 22 of whom received bolus doses of ketamine, with 127 doses analyzed. Demographics, patient, and injury characteristics were similar between patients who did versus did not receive ketamine boluses. In analysis of the subset of ketamine doses used only for sedation, there was no significant difference in ICP or CPP from baseline. Eighteen ketamine doses were given during ICP crises in 11 patients. ICP decreased following these doses and threshold-subtracted CPP rose. CONCLUSIONS: In this retrospective, exploratory study, ICP did not increase following ketamine administration. In the setting of a guidelines-based protocol, ketamine was associated with a reduction in ICP during ICP crises. If these findings are reproduced in a larger study, ketamine may warrant consideration as a treatment for intracranial hypertension in children with severe TBI.


Subject(s)
Brain Injuries, Traumatic , Intracranial Hypertension , Ketamine , Humans , Child , Ketamine/pharmacology , Ketamine/therapeutic use , Retrospective Studies , Intracranial Pressure/physiology , Cerebrovascular Circulation , Brain Injuries, Traumatic/complications , Brain Injuries, Traumatic/drug therapy , Intracranial Hypertension/drug therapy , Intracranial Hypertension/etiology
10.
Phys Chem Chem Phys ; 25(2): 1363-1371, 2023 Jan 04.
Article in English | MEDLINE | ID: mdl-36537612

ABSTRACT

Two diastereomeric dibenzo[a,c]phenazine 1,2-cyclohexyl bridged diesters were prepared and their phase properties examined. While the trans dimer exhibited a broad columnar liquid crystal phase, the cis dimer was amorphous at all temperatures studied. This difference was attributed to the conformational dynamics of the two systems. NMR and DFT studies indicate that both dimers adopt folded and unfolded conformers in solution. While their folded geometries were similar, the trans dimer adopts an extended, largely planar structure, whereas the cis dimer is limited to non-planar unfolded structures and likely disrupts columnar ordering. Geometric constraints imposed by the cylcic linker were also important for columnar stability, with the trans dimer clearing 40 °C lower than the corresponding acyclic 2R,3R-butyl linked dimer, likely because the cyclohexyl group hinders π-π stacking in the unfolded conformation of the former.


Subject(s)
Molecular Conformation , Temperature
11.
J Neurosurg Pediatr ; : 1-8, 2022 Jul 01.
Article in English | MEDLINE | ID: mdl-35901741

ABSTRACT

OBJECTIVE: Isolated linear skull fractures without intracranial findings rarely require urgent neurosurgical intervention. A multidisciplinary fracture management protocol based on antiemetic usage was implemented at our American College of Surgeons-verified level 1 pediatric trauma center on July 1, 2019. This study evaluated protocol safety and efficacy. METHODS: Children younger than 18 years with an ICD-10 code for linear skull fracture without acute intracranial abnormality on head CT were compared before and after protocol implementation. The preprotocol cohort was defined as children who presented between July 1, 2015, and December 31, 2017; the postprotocol cohort was defined as those who presented between July 1, 2019, and July 1, 2020. RESULTS: The preprotocol and postprotocol cohorts included 162 and 82 children, respectively. Overall, 57% were male, and the median (interquartile range) age was 9.1 (4.8-25.0) months. The cohorts did not differ significantly in terms of sex (p = 0.1) or age (p = 0.8). Falls were the most common mechanism of injury (193 patients [79%]). After protocol implementation, there was a relative increase in patients who fell from a height > 3 feet (10% to 29%, p < 0.001) and those with no reported injury mechanism (12% to 16%, p < 0.001). The neurosurgery department was consulted for 86% and 44% of preprotocol and postprotocol cases, respectively (p < 0.001). Trauma consultations and consultations for abusive head trauma did not significantly change (p = 0.2 and p = 0.1, respectively). Admission rate significantly decreased (52% to 38%, p = 0.04), and the 72-hour emergency department revisit rate trended down but was not statistically significant (2.8/year to 1/year, p = 0.2). No deaths occurred, and no inpatient neurosurgical procedures were performed. CONCLUSIONS: Protocolization of isolated linear skull fracture management is safe and feasible at a high-volume level 1 pediatric trauma center. Neurosurgical consultation can be prioritized for select patients. Further investigation into criteria for admission, need for interfacility transfers, and healthcare costs is warranted.

12.
J Org Chem ; 86(21): 15076-15084, 2021 11 05.
Article in English | MEDLINE | ID: mdl-34672594

ABSTRACT

Although discotic liquid crystal dimers have been widely targeted as organic semiconductors and as LC-glass formers, the role of conformational dynamics on the self-assembly of these flexible mesogens remains poorly understood. In an effort to probe this effect, we investigated the impact of linker stereochemistry on the phase behavior of discotic liquid crystalline dimers. Diastereomeric dibenzo[a,c]phenazine diesters were prepared from (2R,3R)- and meso-2,3-butanediol. While both dimers form columnar phases, the meso-isomer had a clearing temperature (Tc) that was 31 °C higher than that of its chiral diastereomer. Conformational analysis via DFT calculations, 1H-NMR, and DOSY experiments indicated that both compounds adopt predominantly extended conformations but that the meso-dimer shows a stronger preference to unfold in solution. To probe how conformation alters phase stability, we prepared derivatives in which catechol and hydroquinone act as rigid linkers that lock the dimers in a folded or an extended conformation, respectively. The diester of hydroquinone possessed a Tc that was nearly 100 °C higher than the catechol derivative, consistent with a model where extended conformations stabilize the LC phase. Extended dimers also exhibited higher transition enthalpies at the Tc, an indication that their columnar phases are more ordered than folded structures.


Subject(s)
Liquid Crystals , Molecular Conformation , Semiconductors , Temperature , Thermodynamics
13.
Pediatr Qual Saf ; 6(5): e456, 2021.
Article in English | MEDLINE | ID: mdl-34476308

ABSTRACT

INTRODUCTION: Many children are discharged from the pediatric emergency department (PED) with incomplete or inappropriate instructions following a concussion. Our objective was to evaluate the effectiveness of a simple intervention in improving discharge instruction disbursement and completeness following PED diagnosis of concussion. METHODS: A pre/post intervention study of 935 patients (375 preintervention and 560 postintervention) ages 5-19, diagnosed with a concussion and discharged from the PED between July 2016 and November 2019, was performed at a single United States pediatric tertiary-care center. Dedicated provider education sessions were held, and a consensus guideline-based set of discharge instructions were implemented in the electronic health record. Primary outcomes included the presence of return-to-play (RTP) instructions, return-to-learn (RTL) instructions, follow-up recommendations, and "complete" discharge (ie, all 3 components present). Statistical process control charts were generated and tested for special cause variation. RESULTS: More patients received instructions for RTP (87% versus 59%) and RTL (60% versus 3%), and a complete discharge was more frequent (45% versus 2%), following the conclusion of the intervention. Only the improvement in RTP instructions was completely sustained into the following academic year, whereas RTL and complete discharge rates declined to 27% and 20%, respectively. CONCLUSIONS: A simple, low-cost intervention such as peer-to-peer education and consensus guideline-based discharge instruction templates can significantly improve discharge readiness after pediatric concussion. Further work is needed to maintain progress and continue improvements, at our large academic trauma center.

14.
J Neurosurg Pediatr ; : 1-13, 2021 Jun 04.
Article in English | MEDLINE | ID: mdl-34087799

ABSTRACT

OBJECTIVE: Pediatric isolated linear skull fractures commonly result from head trauma and rarely require surgery, yet patients are often admitted to the hospital-a costly care plan. In this study, the authors utilized a national database to investigate trends in admission for skull fractures across the United States. METHODS: Children younger than 18 years with isolated linear skull fracture, according to ICD-9 diagnosis codes in the Kids' Inpatient Database of the Healthcare and Utilization Project (HCUP), who presented between 2003 and 2016 were included. HCUP collected data in 2003, 2006, 2009, 2012, and 2016. Children with a depressed skull fracture, multiple traumatic injuries, and acute intracranial findings were excluded. Sample-level data were translated into population-level data by using an HCUP-specific discharge weight. RESULTS: Overall, 11,355 patients (64% males) were admitted to 1605 hospitals. National admissions decreased from 3053 patients in 2003 to 1203 in 2016. The mean ± SD age at admission also decreased from 6.3 ± 5.9 years to 1.2 ± 3.0 years (p < 0.001). The proportion of patients in the lowest quartile of median household income increased by 9%, while that in the highest income quartile decreased by 7% (p < 0.001). Admission was generally more common in the summer months (June, July, and August) and on weekdays (68%). The mean ± SD hospital length of stay decreased from 2.0 ± 3.1 days to 1.4 ± 1.4 days between 2003 and 2012, and then increased to 2.1 ± 6.8 days in 2016 (p < 0.001). When adjusted for inflation, the mean total hospital charges increased from $13,099 to $21,204 (p < 0.001). The greatest proportion of admissions was in the South (35%), and the lowest was in the Northeast (17%). The proportion of patients admitted to large hospitals increased (59% to 72%, p < 0.001), which corresponded to a decrease in patients admitted to small hospitals (16% to 9%, p < 0.001). Overall, the total proportion of admissions to rural hospitals decreased by 6%, and that to urban teaching centers increased by 15% (p < 0.001). Since 2003, no child has undergone a neurosurgical procedure or died as an inpatient. CONCLUSIONS: This study identified a general nationwide decrease in admissions for pediatric linear isolated skull fracture, but associated costs increased. Admissions became less common at smaller rural hospitals and more common at larger urban teaching hospitals. This patient population required no inpatient neurosurgical intervention after 2003.

15.
Nurs Outlook ; 68(5): 626-636, 2020.
Article in English | MEDLINE | ID: mdl-32739096

ABSTRACT

BACKGROUND: High-value healthcare focuses on improving healthcare to produce cost effective care, however limited information on the role of advanced practice registered nurses (APRNs) exists. PURPOSE: This descriptive report describes APRN-led initiatives implemented as part of a national collaborative promoting the Choosing Wisely® campaign and high-value care measures. METHOD: An APRN national collaborative focuses on developing and implementing high-value care initiatives. Monthly calls, podcasts, and a file sharing platform are used to facilitate the work of the national collaborative. FINDINGS: A total of 16 APRN teams from 14 states are participating and have implemented a number of initiatives to reduce unnecessary testing and treatments, promote appropriate antibiotic use, and promote optimal clinical practices such as mobility for hospitalized elderly patients, among others. DISCUSSION: A national collaborative has proven to be a successful way to engage APRN teams to focus on targeting high-value care and promoting evidence-based practices in clinical care.


Subject(s)
Advanced Practice Nursing , Diffusion of Innovation , Health Care Reform , Nurse's Role , Aged , Delivery of Health Care , Humans
16.
Soft Matter ; 15(48): 10035-10044, 2019 Dec 11.
Article in English | MEDLINE | ID: mdl-31789336

ABSTRACT

The effect of incorporating a single amide group on the self-assembly of discotic mesogens was examined. Two series of tetraalkoxydibenzophenazines amides were prepared: tertiary diethyl amides, dEt(n) incapable of hydrogen bonding, and secondary amides HBu(n) that can act as both H-bond donors and acceptors. These compounds exhibit markedly different behavior in solution; NMR studies of dEt(n) show no evidence of self-association, whereas HBu(n) strongly associate via H-bonding and π-stacking. Compounds HBu(n) also act as small molecule gelators in a range of solvents, a property not observed for the corresponding tertiary amides. All compounds were found to form Colh liquid crystal phases; variable temperature XRD experiments indicate that each column has a diameter approximately equal to that of a single molecule. A comparison of the phase behavior of HBu(n) and dEt(n) suggests that the columnar phases of the former are stabilized by hydrogen bonding, likely at the expense of local parallel alignment of these molecules. Single crystal X-ray diffraction studies revealed that dEt(6) adopts an antiparallel arrangement in the solid state, in keeping with previous theories of packing within columnar LC phases. These studies highlight the interplay between competing factors, such as hydrogen bonding, π-stacking and dipole-dipole interactions that affect the stability of the LC phases.

18.
Materials (Basel) ; 12(14)2019 Jul 19.
Article in English | MEDLINE | ID: mdl-31331059

ABSTRACT

Liquid crystalline self-assembly offers the potential to create highly ordered, uniformly aligned, and defect-free thin-film organic semiconductors. Analogues of one of the more promising classes of liquid crystal semiconductors, 5,5"-dialkyl-α-terthiophenes, were prepared in order to investigate the effects of replacing the central thiophene with either an oxadiazole or a thiadiazole ring. The phase behaviour was examined by differential scanning calorimetry, polarized optical microscopy, and variable temperature x-ray diffraction. While the oxadiazole derivative was not liquid crystalline, thiadiazole derivatives formed smectic C and soft crystal lamellar phases, and maintained lamellar order down to room temperature. Variation of the terminal alkyl chains also influenced the observed phase sequence. Single crystal structures revealed the face-to-face orientation of molecules within the layers in the solid-state, a packing motif that is rationalized based on the shape and dipole of the thiadiazole ring, as corroborated by density functional theory (DFT) calculations. The solution opto-electronic properties of the systems were characterized by absorption and emission spectroscopy, cyclic voltammetry, and time-dependent density functional theory (TD-DFT).

19.
J Neurosurg Pediatr ; 24(2): 145-152, 2019 May 31.
Article in English | MEDLINE | ID: mdl-31151096

ABSTRACT

OBJECTIVE: Open and endoscope-assisted repair are surgical options for sagittal craniosynostosis, with limited research evaluating each technique's immediate and long-term costs. This study investigates the cost-effectiveness of open and endoscope-assisted repair for single, sagittal suture craniosynostosis. METHODS: The authors performed a retrospective cohort study of patients undergoing single, sagittal suture craniosynostosis repair (open in 17 cases, endoscope-assisted in 16) at less than 1 year of age at Monroe Carell Jr. Children's Hospital at Vanderbilt (MCJCHV) between August 2015 and August 2017. Follow-up data were collected/analyzed for 1 year after discharge. Surgical and follow-up costs were derived by merging MCJCHV financial data with each patient's electronic medical record (EMR) and were adjusted for inflation using the healthcare Producer Price Index. Proxy helmet costs were derived from third-party out-of-pocket helmet prices. To account for variable costs and probabilities, overall costs were calculated using TreeAge tree diagram software. RESULTS: Open repair occurred in older patients (mean age 5.69 vs 2.96 months, p < 0.001) and required more operating room time (median 203 vs 145 minutes, p < 0.001), more ICU days (median 3 vs 1 day, p < 0.001), more hospital days (median 4 vs 1 day, p < 0.001), and more frequently required transfusion (88% vs 6% of cases). Compared to patients who underwent open surgery, patients who underwent endoscopically assisted surgery more often required postoperative orthotic helmets (100% vs 6%), had a similar number of follow-up clinic visits (median 3 vs 3 visits, p = 0.487) and CT scans (median 3 vs 2 scans), and fewer emergency department visits (median 1 vs 3 visits). The TreeAge diagram showed that, overall, open repair was 73% more expensive than endoscope-assisted repair ($31,314.10 vs $18,081.47). Sensitivity analysis identified surgical/hospital costs for open repair (mean $30,475, SEM $547) versus endoscope-assisted repair (mean $13,746, SEM $833) (p < 0.001) as the most important determinants of overall cost. Two-way sensitivity analysis comparing initial surgical/hospital costs confirmed that open repair remains significantly more expensive under even worst-case initial repair scenarios ($3254.81 minimum difference). No major surgical complications or surgical revisions occurred in either cohort. CONCLUSIONS: The results of this study suggest that endoscope-assisted craniosynostosis repair is significantly more cost-effective than open repair, based on markedly lower costs and similar outcomes, and that the difference in initial surgical/hospital costs far outweighs the difference in subsequent costs associated with helmet therapy and outpatient management, although independent replication in a multicenter study is needed for confirmation due to practice and cost variation across institutions. Longer-term results will also be needed to examine whether cost differences are maintained.

20.
Chem Commun (Camb) ; 55(47): 6696-6699, 2019 Jun 06.
Article in English | MEDLINE | ID: mdl-31062005

ABSTRACT

The facile tuning of near-infrared absorption of manganese(iii) phthalocyanines was accomplished by changing the nature and number of bound axial ligands. For a series of axial ligands on manganese α-octabutoxyphthalocyanine and α-octakis-(isopropylthio)phthalocyanine, the electron density on the metal and its displacement from the Pc-ring plane both control the position of the complex's Q-band. For these two macrocycles, this strong absorption band could be tuned over a λmax range of 815-948 nm by axial ligand exchange.

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