Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0 eV.

Nutrient-efficient catfish-based aquaponics for producing lamb's lettuce at two light intensities.

BACKGROUND: Aquaponic systems are sustainable processes of managing water and nutrients for food production. An innovate nutrient-efficient catfish-based (Clarias gariepinus) aquaponics system was implemented for producing two cultivars of two leafy vegetables largely consumed worldwide: lamb's lettuce (Valerianella locusta var. Favor and Valerianella locusta var. de Hollande) and arugula (Eruca vesicaria var. sativa and Eruca sativa). Different growing treatments (4 × 2 factorial design) were applied to plants of each cultivar, grown at two light intensities (120 and 400 µmol m-2 s-1). During growth, several morphological characteristics (root length, plant height, leaf number, foliage diameter and biggest leaf length) were measured. At harvest, plants were weighed and examined qualitatively in terms of greenness and health status. Additionally, leaf extracts were obtained and used to determine total phenolic contents, antioxidant capacities, and levels of cytotoxicity to Caco-2 intestinal model cells. RESULTS: After a 5-week growth period, both lamb's lettuce cultivars presented high levels of greenness and health status, at both light intensities, particularly the var. de Hollande that also showed higher average performance in terms of plant morphology. In turn, arugula cultivars showed lower levels of greenness and health status, especially the cultivar E. vesicaria var. sativa submitted to direct sunlight during growth. In addition, plant specimens submitted to higher levels of light intensity showed higher contents in antioxidants/polyphenols. Cultivars with a higher content in antioxidants/polyphenols led to higher Caco-2 cell viability. CONCLUSION: For successful industrial implementation of the aquaponics technology, different and optimized acclimatizing conditions must be applied to different plant species and cultivars. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Percutaneous left stellate ganglion block for refractory ventricular tachycardia in structural heart disease: our single-centre experience.

INTRODUCTION: When electrical storm (ES) is amenable to neither antiarrhythmic drugs, nor deep sedation or catheter ablation, autonomic modulation may be considered. We report our experience with percutaneous left stellate ganglion block (PSGB) to temporarily suppress refractory ventricular arrhythmia (VA) in patients with structural heart disease. METHODS: A retrospective analysis was performed at our institution of patients with structural heart disease and an implantable cardioverter defibrillator (ICD) who had undergone PSGB for refractory VA between January 2018 and October 2021. The number of times antitachycardia pacing (ATP) was delivered and the number of ICD shocks/external cardioversions performed in the week before and after PSGB were evaluated. Charts were checked for potential complications. RESULTS: Twelve patients were identified who underwent a combined total of 15 PSGB and 5 surgical left cardiac sympathetic denervation procedures. Mean age was 73 ± 5.8 years and all patients were male. Nine of 12 (75%) had ischaemic cardiomyopathy, with the remainder having non-ischaemic dilated cardiomyopathy. Mean left ventricular ejection fraction was 35% (±â€¯12.2%). Eight of 12 (66.7%) patients were already being treated with both amiodarone and beta-blockers. The reduction in ATP did not reach statistical significance (p = 0.066); however, ICD shocks (p = 0.028) and ATP/shocks combined were significantly reduced (p = 0.04). At our follow-up electrophysiology meetings PSGB was deemed ineffective in 4 of 12 patients (33%). Temporary anisocoria was seen in 2 of 12 (17%) patients, and temporary hypotension and hoarseness were reported in a single patient. DISCUSSION: In this limited series, PSGB showed promise as a method for temporarily stabilising refractory VA and ES in a cohort of male patients with structural heart disease. The side effects observed were mild and temporary.

Stark control of multiphoton ionization through Freeman resonances in alkyl iodides.

Multiphoton ionization (MPI) of alkyl iodides (RI, R = CnH2n+1, n = 1-4) has been investigated with femtosecond laser pulses centered at 800 and 400 nm along with photoelectron imaging detection. In addition, the ultraviolet (UV)-vacuum ultraviolet (VUV) absorption spectra of gas-phase RIs have been measured in the photon energy range of 5-11 eV using the VUV Fourier transform spectrometer at the VUV DESIRS beamline of the synchrotron SOLEIL facility. The use of high-laser-field strengths in matter-radiation interaction generates highly non-linear phenomena, such as the Stark shift effect, which distorts the potential energy surfaces of molecules by varying both the energy of electronic and rovibrational states and their ionization energies. The Stark shift can then generate resonances between intermediate states and an integer number of laser photons of a given wavelength, which are commonly known as Freeman resonances. Here, we study how the molecular structure of linear and branched alkyl iodides affects the UV-VUV absorption spectrum, the MPI process, and the generation of Freeman resonances. The obtained results reveal a dominant resonance in the experiments at 800 nm, which counter-intuitively appears at the same photoelectron kinetic energy in the whole alkyl iodide series. The ionization pathways of this resonance strongly involve the 6p(2E3/2) Rydberg state with different degrees of vibrational excitation, revealing an energy compensation effect as the R-chain complexity increases.

Proximal seal dilatation following fenestrated endovascular repair for complex abdominal aortic aneurysms.

OBJECTIVE: Although proximal neck dilatation following infrarenal endovascular aneurysm repair (EVAR) is common and is associated with proximal graft failure, little is known about sealing zone dilatation and its clinical relevance following fenestrated EVAR (FEVAR). We studied proximal seal dilatation (PSD) dynamics following FEVAR and assessed its clinical significance. METHODS: We included all consecutive patients treated for a juxta-/supra-renal aneurysm with fenestrated EVAR using the Zenith Fenestrated Endovascular Graft (Cook Medical, Bloomington, Ind) from 2008 to 2018 in two large teaching hospitals in the Netherlands. The primary outcome was PSD over time and was determined using a linear mixed-effects model. Secondary outcomes included associations for early PSD and difference in aortic dilatation at the level of the covered stent compared with the bare stent. Proximal seal-related adverse events were also obtained. RESULTS: Our cohort included 84 patients with a median computed tomography angiography follow-up time of 24.5 months (interquartile range [IQR], 17-42 months). Maximum aneurysm diameter was 60.1 mm (IQR, 56.9-67.2 mm). Mean proximal seal diameter at baseline was 26.2 mm (standard deviation [SD], ±2.8 mm), mean stent oversizing was 20.1% (SD, ±9.1%), and mean proximal seal length was 29.5 mm (SD, ±11.7 mm). Proximal seal dilatation of 1.7 mm (95% confidence interval [CI], 1.4-2.1 mm) was found in the first year, decelerating thereafter (second year, 0.9 mm/year; 95% CI, 0.7-1.1 mm/y). Over 10% PSD at 1 year occurred in 22 patients (27%) and was associated with stent graft oversizing (odds ratio, 1.1; 95% CI, 1.03-1.2; P = .008) and a lower number of target vessels (four fenestrations/ref two fenestrations: odds ratio, 0.13; 95% CI, 0.02-0.74; P = .029). At last available imaging, dilatation difference was higher at the level of the covered stent compared with the bare stent (3.0 mm [IQR, 1.3-5.1 mm] vs 1.6 mm [IQR, 0.8-2.5 mm]; P < .001). During the study period, only one patient (1.2%) developed a proximal seal-related adverse event (type IA endoleak). CONCLUSIONS: PSD is present following FEVAR, occurring at a faster rate in the first year and subsequently decelerating thereafter, similarly to neck dilatation after standard infrarenal EVAR. Although its clinical implication seems to remain limited in the first years following implantation, further research is required to assess the effect of PSD on long-term FEVAR outcomes.

Imaging the Photodissociation Dynamics and Fragment Alignment of CH2BrI at 193 nm.

The photodissociation dynamics and photofragment alignment of bromoiodomethane (CH2BrI) have been studied at 193 nm using a double experimental and theoretical approach. In addition, the ultraviolet (UV)-vacuum ultraviolet (VUV) absorption spectrum of gas phase CH2BrI has been measured in the photon energy range of 5-11 eV using the VUV Fourier transform spectrometer (FTS) at the VUV beamline DESIRS of the synchrotron SOLEIL facility. The slice imaging technique in combination with resonance enhanced multiphoton ionization (REMPI) detection of the Br(2PJ) and I(2PJ) (with J = 3/2 and 1/2 for Br/I and Br*/I*, respectively) atomic photofragments have been used to produce experimental translational energy and angular distributions, which were analyzed to deliver, on one hand, the partitioning of the available energy among the different degrees-of-freedom of the photofragments and, on the other, the photofragment polarization in terms of aqk(p) alignment parameters. The experimental measurements were rationalized in terms of high-level ab initio calculations of vertical excitation energies, transition dipole moments and potential energy curves (PECs) along different reaction coordinates to provide a complete picture of the photodissociation dynamics. The results indicate that for excitation at 193 nm, prompt C-X cleavage (with X being either halogen atom, Br or I) competes with fast internal conversion and consequent stochastic dissociation in lower electronic states. In the case of the CH2Br + I(2P3/2)/I*(2P1/2) channels, the dynamics are greatly biased toward the stochastic dissociation process due to both the particular PECs landscape and the unfavored excitation of the CH2BrI ensemble with respect to the C-I molecular axis at this excitation energy. The ab initio PECs provide a tentative path for the fast dissociation process in either case. For the C-Br bond breakage, excitation to the 13A' electronic state and predissociation through the 11A'/11A″ or 12A'/12A″ states, leading to direct dissociation through the 10A'/9A″ states, appear as the most consistent dynamics. For the C-I channel, predissociation does not become a reliable possibility and a fast internal conversion may precede dissociation through the repulsive 6A'/6A″ and 4A'/4A″ states. The large content of rotational and vibrational excitation of the polyatomic cofragments is justified through the soft impulsive model and the geometrical changes produced along the dissociation pathway. Strikingly, the aqk(p) alignment parameters obtained for the Br(2P3/2) and I(2P3/2) photoproducts indicate that the rotational angular momentum of the CH2X (X = I or Br) cofragment appears highly constrained along the recoil direction. Finally, this work presents a highly plausible explanation for the branching ratio of secondary dissociation processes in the photodynamics of CH2BrI at 193 nm.

MicroRNAs expression profiles in early responses to different levels of water deficit in Setaria viridis.

Water deficit is a major constraint for crops of economic importance in almost all agricultural regions. However, plants have an active defense system to adapt to these adverse conditions, acting in the reprogramming of gene expression responsible for encoding microRNAs (miRNAs). These miRNAs promote the regulation to the target gene expression by the post-transcriptional (PTGS) and transcriptional gene silencing (TGS), modulating several pathways including defense response to water deficit. The broader knowledge of the miRNA expression profile and its regulatory networks in response to water deficit can provide evidence for the development of new biotechnological tools for genetic improvement of several important crops. In this study, we used Setaria viridis accession A10.1 as a C4 model plant to widely investigate the miRNA expression profile in early responses to different levels of water deficit. Ecophysiological studies in Setaria viridis under water deficit and after rewatering demonstrated a drought tolerant accession, capable of a rapid recovery from the stress. Deep small RNA sequencing and degradome studies were performed in plants submitted to drought to identify differentially expressed miRNA genes and their predicted targets, using in silico analysis. Our findings showed that several miRNAs were differentially modulated in response to distinctive levels of water deficit and after rewatering. The predicted mRNA targets mainly corresponded to genes related to cell wall remodeling, antioxidant system and drought-related transcription factors, indicating that these genes are rapidly regulated in early responses to drought stress. The implications of these modulations are extensively discussed, and higher-effect miRNAs are suggested as major players for potential use in genetic engineering to improve drought tolerance in economically important crops, such as sugarcane, maize, and sorghum. Supplementary Information: The online version contains supplementary material available at 10.1007/s12298-022-01226-z.

Aneurysm Volumes After Endovascular Repair of Ruptured vs Intact Aortic Aneurysms: A Retrospective Observational Study.

PURPOSE: To compare changes in abdominal aortic aneurysm (AAA) sac volume between endovascular aneurysm repairs (EVAR) performed for ruptured (rEVAR) vs intact (iEVAR) AAAs and to determine the impact of early volume shrinkage on future complications. MATERIALS AND METHODS: A retrospective analysis was performed of all patients undergoing standard infrarenal EVAR from 2002 to 2016 at a tertiary referral institution. Only patients with degenerative AAAs and with 30-day and 1-year computed tomography angiography (CTA) imaging were included. Early sac shrinkage was defined as a volume sac reduction >10% between the first (<30-day) and the 1-year CTA. The primary endpoint was to compare AAA sac volume changes between patients undergoing rEVAR (n=51; mean age 71.0±8.5 years; 46 men) vs iEVAR (n=393; mean age 72.3±7.5 years; 350 men). Results are reported as the mean difference with the interquartile range (IQR Q1, Q3). The secondary endpoint was freedom from aneurysm-related complications after 1 year as determined by regression analysis; the results are presented as the hazard ratio (HR) and 95% confidence interval (CI). RESULTS: At baseline, the rEVAR group had larger aneurysms (p<0.001) and shorter (p<0.001) and more angulated (p=0.028) necks. Aneurysm sac volume decreased more in the rEVAR group during the first year [-26.3% (IQR -38.8%, -12.5%)] vs the iEVAR group [-11.9% (IQR -27.5%, 0); p<0.001]. However, after the first year, the change in sac volume was similar between the groups [-3.8% (IQR -32.9%, 31.9%) for rEVAR and -1.5% (IQR -20.9%, 13.6%) for iEVAR, p=0.74]. Endoleak occurrence during follow-up was similar between the groups. In the overall population, patients with early sac shrinkage had a lower incidence of complications after the 1-year examination (adjusted HR 0.59, 95% CI 0.39 to 0.89, p=0.01). CONCLUSION: EVAR patients treated for rupture have more pronounced aneurysm sac shrinkage compared with iEVAR patients during the first year after EVAR. Patients presenting with early shrinkage are less likely to encounter late complications. These parameters may be considered when tailoring surveillance protocols.

Long Term Outcomes of Post-Implantation Syndrome After Endovascular Aneurysm Repair.

OBJECTIVE: The aim of this study was to investigate the association between post-implantation syndrome (PIS) and long term outcomes, with emphasis on cardiovascular prognosis. METHODS: One hundred and forty-nine consecutive patients undergoing EVAR in a tertiary institution were previously included in a study investigating the risk factors and short term consequences of PIS (defined as tympanic temperature ≥ 38°C and CRP > 10 mg/L, after excluding complications with an effect on inflammatory markers). This study was based on a prospectively maintained database. Survival status was derived from inquiry of civil registry database information and causes of death from the Dutch Central Bureau of Statistics. The primary endpoint was cardiovascular events. Secondary endpoints were overall and specific cause mortality (cardiovascular, ischaemic heart disease, AAA, and cancer related mortality). Aneurysm sac dynamics and occurrence of endoleaks were also analysed. Survival estimates were obtained using Kaplan-Meier plots and a multivariable model was constructed to correct for confounders. RESULTS: The PIS incidence was 39% (58/149). At the time of surgery, patients had a mean age of 73 ± 7 years and were predominantly male. There were no baseline differences between the PIS and non-PIS groups. The median follow up was 6.4 years (3.2 - 8.3), similar in both groups (p = .81). There was no difference in cardiovascular events for PIS and non-PIS patients (p = .63). However, Kaplan-Meier plots suggest a trend towards a higher rate of cardiovascular events in PIS patients during the first years: freedom from cardiovascular events at one year was 94% vs. 89% and at three years 90% vs. 82%. No differences were found in overall and specific cause mortality. There was a higher rate of type II endoleaks for non-PIS patients (28% vs. 9%, p = .005). Sac dynamics were similar in both groups. CONCLUSION: The results suggest that PIS is not associated with a statistically significantly higher risk of cardiovascular events. PIS had no impact on mortality. Lastly, PIS patients had fewer type II endoleaks, but sac dynamics were analogous.

Risk Factors, Dynamics, and Clinical Consequences of Aortic Neck Dilatation after Standard Endovascular Aneurysm Repair.

OBJECTIVE: Aortic neck dilatation (AND) occurs after endovascular aneurysm repair (EVAR) with self expanding stent grafts (SESs). Whether it continues, ultimately exceeding the endograft diameter leading to abdominal aortic aneurysm (AAA) rupture, remains uncertain. Dynamics, risk factors, and clinical relevance of AND were investigated after EVAR with standard SESs. METHODS: All intact EVAR patients treated from 2000 to 2015 at a tertiary institution were included. Demographic, anatomical, and device related characteristics were investigated as risk factors for AND. Outer to outer diameters were measured at a single standardised aortic level on reconstructed computed tomography (CT) images. RESULTS: A total of 460 patients were included (median follow up 5.2 years, interquartile range [IQR] 3.0, 7.7 years; CT imaging follow up 3.3 years, IQR 1.3, 5.4). Baseline neck diameter was 24 mm (IQR 22, 26) and increased 11.1% (IQR 1.5%, 21.9%) at last CT imaging. Endograft oversizing was 20.0% (IQR 13.6, 28.0). AND was greater during the first year (5.2% [IQR 0, 11.7]) decreasing subsequently (two to four years to 1.4%/year [IQR 0.0, 4.5%], p ≤ .001) and was associated with suprarenal fixation endografts (t value = 7.9, p < .001) and oversizing (t value = 4.4, p < .001). AND exceeding the endograft was 3.5% (95% CI 2.2% - 4.8%) and 14.4% (95% CI 11.0% - 17.8%) at five and eight years, respectively. Excessive AND was associated with baseline neck diameter (OR 1.2/mm, 95% CI 1.05 - 1.41) while the Excluder endograft had a protective effect (OR 0.15, 95% CI 0.04 - 0.58). Excessive AND was associated with type 1A endoleak (HR 3.3, 95% CI 1.1 - 9.7) and endograft migration > 5 mm (HR 3.1, 95% CI 1.4 - 6.9). CONCLUSION: AND after EVAR with SES is associated with endograft oversizing and radial force but decelerates after the first post-operative year. Baseline aortic neck diameter and suprarenal stent bearing endografts were associated with an increased risk of AND beyond nominal stent graft diameter. However, it remains unclear whether patient selection, differences in endograft radial force or the suprarenal stent are accountable for this difference.

Pantaloon Vein Grafts - An Alternative Fix for an Old Problem.

BACKGROUND: Pantaloon vein grafts (PVG) were first used to replace infrarenal aortic grafts. However, they may have other applications, such as femoral aortic bifurcation reconstruction. METHODS: We herein present 2 different cases, the first with a prosthetic graft infection at the recipient femoral bifurcation, the second for a late occlusion of the femoral bifurcation following endarterectomy and prosthetic patch closure, who were treated with PVG fashioned from the ipsilateral great saphenous vein. CONCLUSION: The use of PVG to reconstruct the femoral bifurcation allowed for concurrent axial and profunda femoris artery revascularization, while correcting diameter mismatch with the inflow source and seem particularly suitable for infected operative fields.

Long-term results after standard endovascular aneurysm repair with the Endurant and Excluder stent grafts.

OBJECTIVE: Many endografts are currently available for standard endovascular repair of infrarenal abdominal aortic aneurysms. Comparison of long-term outcomes between devices might aid in this decision process, but comparative data are scarce. The purpose of this study was to report long-term clinical outcomes of two commercially available endoprosthesis, the Endurant (Medtronic Vascular, Inc, Minneapolis, Minn) and the Excluder (W. L. Gore & Associates, Flagstaff, Ariz) stent grafts. METHODS: Patients undergoing standard endovascular repair from July 2004 to December 2011 in a single institution with the Endurant or the Low-Porosity Excluder endografts were eligible. Only patients treated for intact degenerative abdominal infrarenal aneurysms were included. All measurements were performed on center-lumen line reconstructions obtained on dedicated software. The primary end point was primary clinical success, defined as clinical success without the need for an additional or secondary surgical or endovascular procedure. Neck-related events (a composite of type IA endoleak, neck-related secondary intervention, or migration of >5 mm), neck morphology changes, renal function, and overall survival were secondary end points. RESULTS: The study included 277 patients (156 Endurants; 121 Excluders). The median follow-up was 5.8 years (range, 0.1-12.4 years) and did not differ between groups (P = .18). Patients treated with the Endurant stent graft had wider (neck diameter of >28 mm, 27.3% vs 1.7% [P < .001]; neck diameter of 27 mm, [interquartile range (IQR), 24-29 mm] for Endurant and 24 mm [IQR, 22-25 mm] for Excluder; P < .001) and more angulated necks (ß-angle of >60°, 26.7% vs 12.5%; P = .004). Oversizing was greater in the Endurant group (16% [IQR, 12%-22%] vs 13% [IQR, 8%-17%], respectively; P < .001). Patients were treated outside device instructions for use regarding proximal neck: 16.7% in the Endurant and 17.3% in the Excluder group (P = .720). The 7-year primary clinical success was 54.7% for the Endurant and 58.1% for the Excluder groups (P = .53). Freedom from neck-related events at 7 years was 76.7% for the Endurant and 78.8% for Excluder group (P = .94). The Endurant stent graft (hazard ratio [HR], 2.7; 95% confidence interval [CI], 1.3-5.8; P = .009) was an independent predictor of significant renal function decline. Neck dilatation was greater in Endurant-implanted patients (13% [95% CI, 2%-22%] vs 4% [95% CI, 0%-10%]; P < .001). Overall survival at 7 years was 61.4% in the Endurant and 50.3% (n = 50; standard error, 0.047) in the Excluder group (P = .39). CONCLUSIONS: This study reveals that durable and sustainable results can be obtained with either of these late generation devices. This finding suggests that careful planning and a tailored device selection taking into account the patient's anatomy are more relevant determinants than the graft model itself to obtain clinical success. The Endurant endoprosthesis seems to be associated with a higher rate of neck dilatation and faster decrease in the estimated glomerular filtration rate, but further studies with longer follow-up are necessary to determine the clinical relevance of these findings.

Comparison of midterm results of endovascular aneurysm repair for ruptured and elective abdominal aortic aneurysms.

OBJECTIVE: Endovascular aneurysm repair (EVAR) became an increasingly preferred modality for abdominal aortic aneurysm (AAA) repair both in elective AAA repair (el-EVAR) and EVAR of a ruptured AAA (r-EVAR) setting. Ruptured AAAs usually have more hostile anatomies and less time for planning. Consequently, more complications may arise after r-EVAR. The purpose of this study was to compare mi-term outcomes between r-EVAR and el-EVAR. METHODS: A retrospective cohort analysis of patients undergoing EVAR from 2000 to 2015 at a tertiary institution was performed. Patients with previous aortic surgery, nonatherosclerotic AAA and isolated iliac aneurysms were excluded. In-hospital casualties or patients who were intraoperatively converted to open repair were also excluded. For the midterm outcome analysis, only patients with at least two postoperative examinations (a 30-day computed tomography scan and a second postoperative examination performed 6 months or later) were considered. The primary end point was freedom from aneurysm-related complications (a composite of type I or III endoleak, aneurysm sac growth, migration of more than 5 mm, device integrity failure, AAA-related death, late postimplant rupture, or AAA-related secondary intervention). Freedom from secondary interventions, neck-related events (defined as a composite of type IA endoleak, migration of more than 5 mm, or preemptive neck-related secondary intervention) and late survival were secondary end points. The impact of device instructions for use (IFU) compliance on neck events was also assessed. RESULTS: The study included 565 patients (65 r-EVAR and 500 el-EVAR). Eighty-two patients were treated outside proximal neck IFU, 13 in the r-EVAR group (21.3%) and 69 (14.5%) in the el-EVAR (P = .16). During the index hospitalization, there were more complications (12.3% vs 3.2%; P = .001) and reinterventions (12.3% vs 2.8%; P < .001) in the r-EVAR group. After discharge, median clinical follow-up time was 4.3 years (interquartile range, 2.1-7.0 years) without differences between both groups. Five-year freedom from AAA-related complications was 53.9% in the r-EVAR group and 65.4% in the el-EVAR (P = .21). In multivariable analysis the r-EVAR group was not at increased risk for late complications (hazard ratio [HR], 0.94; 95% confidence interval [CI], 0.54-1.61; P = .81). Five-year freedom from neck-related events was 74% in r-EVAR and 82% in the el-EVAR group (P = .345). Patients treated outside neck IFU were at greater risk for neck-related events both in r-EVAR (HR, 6.5; 95% CI, 1.8-22.9; P = .004) and el-EVAR group (HR, 2.6; 95% CI, 1.5-4.5; P < .001). Freedom from secondary interventions at 5 years was 63.0% for r-EVAR and 76.9% for el-EVAR (P = .16). Survival at 5 years was 68.8% in the r-EVAR group and 73.3% in the el-EVAR group (P = .30). CONCLUSIONS: Durable and sustainable midterm outcomes were found for both r-EVAR and el-EVAR patients who survived the postoperative period. Patients treated outside the IFU are at greater risk for late complications. Surveillance protocols may be tailored according to individual anatomy and IFU compliance rather than timing of repair.

Experimental and Theoretical Investigation of the 3sp(d) Rydberg States of Fenchone by Polarized Laser Resonance-Enhanced-Multiphoton-Ionization and Fourier Transform VUV Absorption Spectroscopy.

The VUV absorption spectrum of fenchone is re-examined using synchrotron radiation Fourier transform spectrometry, revealing new vibrational structure. Picosecond laser (2+1) resonance enhanced multiphoton ionization (REMPI) spectroscopy complements this, providing an alternative view of the 3spd Rydberg excitation region. These spectra display broadly similar appearance, with minor differences that are largely explained by referring to calculated one- and two-photon electronic excitation cross-sections. Both show good agreement with Franck-Condon simulations of the relevant vibrational structures. Parent ion REMPI ionization yields with both femtosecond and picosecond excitation laser pulses are studied as a function of laser polarization and intensity, the latter providing insight into the relative two-photon excitation and one-photon ionization rates. The experimental circular-linear dichroism observed in the parent ion yields varies strongly between the 3s and 3p Rydberg states, in good overall agreement with the calculated two-photon excitation circular-linear dichroism, while corroborating other evidence that the 3pz sub-state plays no more than a very minor role in the (2+1) REMPI spectrum. Vibrationally resolved photoelectron spectra are recorded with picosecond pulse duration (2+1) REMPI at selected intermediate vibrational excitations. The 3s intermediate state displays a very strong Δv=0 propensity on ionization, but the 3p intermediate evidences more complex vibronic dynamics, and we infer some 3p→3s internal conversion prior to ionization.

Total Luminal Volume Predicts Risk after Endovascular Aneurysm Repair.

OBJECTIVE: Large aneurysm diameter represents a well known predictor of late complications after endovascular aneurysm repair (EVAR). However, the role of the thrombus free lumen inside the abdominal aortic aneurysm (AAA) sac is not clear. It was hypothesised that greater luminal volume represents a relevant risk factor for late complications after EVAR. METHODS: A retrospective cohort analysis was performed including all patients undergoing EVAR from 2005 to 2016 at a tertiary referral institution. Pre-operative AAA lumen volume was measured in centre lumen line reconstructions and patients were stratified into quartiles according to luminal volume. The primary endpoint was freedom from AAA related complications. Secondary endpoints were freedom from neck events (type 1A endoleak, migration >5 mm or any pre-emptive neck related intervention), iliac related events (type 1B endoleak or pre-emptive iliac related intervention), and overall survival. RESULTS: Four hundred and four patients were included: 101 in the first quartile (Q1; <61 cm3). Patients with higher luminal volumes had wider, shorter, and more angulated proximal necks. There were more ruptured AAAs, more aorto-uni-iliac implanted devices and patients outside neck instructions for use in the 4th quartile. Five year freedom from AAA related complications was 79%, 66%, 58% and 56%, respectively (p = .007). At five years, freedom from neck related events was 86%, 84%, 73%, and 71%, respectively, for the four groups (p = .009), and freedom from iliac related events was 96%, 91%, 88%, and 88%, respectively (p = .335). On multivariable analysis, luminal volume was an independent predictor of late complications (Q4 vs. Q1 - hazard ratio: 1.91, 95% confidence interval 1.01-3.6, p = .046). Overall survival at five years was not affected by lumen volume (p = .75). CONCLUSION: AAA luminal volume represents an important risk factor for AAA related complications. This information may be considered when deciding tailoring surveillance protocols after EVAR. However, larger studies are needed to validate this hypothesis.

Vacuum-Ultraviolet Absorption Spectrum of 3-Methoxyacrylonitrile.

The high-resolution absorption spectrum of 3-methoxyacrylonitrile (3MAN) was measured between 5.27 and 12.59 eV using a synchrotron-based Fourier-transform spectrometer. It was related to an absolute absorption cross-section scale. Complementary calculations at the DFT-MRCI/aug-cc-pVTZ level of theory document the vertical transition energies and oscillator strengths toward the first 19 states of both the E and Z geometrical isomers of 3MAN. Comparisons with the experimental absorption spectrum reveal the similarities and differences between 3MAN, a bifunctional molecule, with acrylonitrile and methylvinylether, where only one functional group is present. As in acrylonitrile, several broad valence transitions were observed up to the ionization limit. They are likely associated with the extended π-system induced by the nitrile group but might also involve σσ* transitions close to the ionization limit. As in methylvinylether, Rydberg series converging to the ionization limit are absent. This is attributed to a difference in neutral and cationic geometry due to a 60° rotation of the methyl group.

High-resolution vacuum ultraviolet absorption spectra of 2,3- and 2,5-dihydrofuran.

Using a synchrotron-based Fourier-transform spectrometer, the high-resolution absorption spectra of the C1-symmetric 2,3-dihydrofuran (23DHF) and C2v-symmetric 2,5-dihydrofuran (25DHF) have been measured from 5.5 eV to 9.4 eV with an absolute absorption cross section scale. Oscillator strengths and vertical excitation energies of the lowest 18 states have been computed using the average of the second- and third-order algebraic diagrammatic construction polarization propagator method and the equation-of-motion coupled-cluster method at the level of singles and doubles model. These show that the bright valence transitions of ππ*-character are embedded into Rydberg transitions, whose oscillator strengths are at least one order of magnitude lower. To account for intensity borrowing, the first broad valence transition between 5.5 eV and 6.8 eV was simulated using a nuclear ensemble, and the agreement between experiment and theory is excellent. Whereas 23DHF only exhibits one broad valence transition followed by d/f Rydberg series converging to the ionization energy, the absorption spectrum of 25DHF has four bands, attributed to a valence nπσ → π*-transition, nπσ → 3px,z/3dxz transitions, a second valence nπ → π*-transition followed by d/f Rydberg series converging to the ionization energy, respectively. All Rydberg series converging to the ionization energy have been characterized in terms of their quantum defects.

Patients with large neck diameter have a higher risk of type IA endoleaks and aneurysm rupture after standard endovascular aneurysm repair.

OBJECTIVE: Standard endovascular aneurysm repair (EVAR) is the most common treatment of abdominal aortic aneurysms (AAAs). EVAR has been increasingly used in patients with hostile neck features. This study investigated the outcomes of EVAR in patients with neck diameters ≥30 mm in the prospectively maintained Endurant Stent Graft Natural Selection Global Postmarket Registry (ENGAGE). METHODS: This is a retrospective study comparing patients with neck diameters ≥30 mm with patients with neck diameters <30 mm. The primary end point was type IA endoleak (EL1A). Secondary end points included secondary interventions to correct EL1A, aneurysm rupture, and survival. RESULTS: This study included 1257 patients (mean age, 73.1 years; 89.4% male) observed for a median 4.0 years (interquartile range, 2.7-4.8 years). A total of 97 (7.7%) patients had infrarenal neck diameters ≥30 mm and were compared with the remaining 1160 (92.3%) with neck diameters <30 mm. At baseline, there were no differences between groups regarding demographics and comorbidities other than cardiac disease, which was more frequent in the ≥30-mm neck diameter group (P = .037). There were no significant differences between the groups regarding neck length, angulation, thrombus, or calcification. Mean preoperative AAA diameter was 64.6 ± 11.3 mm in the ≥30-mm neck diameter group and 60.0 ± 11.6 mm in the <30-mm neck diameter group (P < .001). Stent graft oversizing was significantly less in the ≥30-mm neck diameter group (12.2% ± 8.9% vs 22.1% ± 11.9%; P <. 001). Five patients (5.2%) in the ≥30-mm neck diameter group and 30 (2.6%) with neck diameters <30 mm developed EL1A, yielding a 4-year freedom from EL1A of 92.4% vs 96.6%, respectively (P = .09). Oversizing was 21.8% ± 13.0% for patients developing EL1A and 21.3% ± 12.4% for the remaining cohort (P = .99). In adjusting for neck length, AAA diameter, and device oversizing, patients with neck diameter ≥30 mm were at greater risk for development of EL1A (hazard ratio, 3.0; 95% confidence interval, 1.0-9.3; P = .05). Secondary interventions due to EL1A did not differ between groups (P = .36). AAA rupture occurred in three patients with neck diameter ≥30 mm (3.1%) and in eight patients with neck diameter <30 mm (0.7%; hazard ratio, 5.1; 95% confidence interval, 1.4-19.2; P = .016); two cases were EL1A related in each group. At 4 years, overall survival was 61.6% for the ≥30-mm neck diameter group and 75.2% for the <30-mm neck diameter group (P = .009), which remained significant on correcting for sex and AAA diameter (P = .016). CONCLUSIONS: In this study, patients with infrarenal neck diameter ≥30 mm had a threefold increased risk of EL1A and fivefold risk of aneurysm rupture after EVAR as well as worse overall survival. This may influence the choice of AAA repair and underlines the need for regular computed tomography-based imaging surveillance in this subset of patients. Furthermore, these results can serve as standards with which new, possibly improved technology, such as EndoAnchors (Medtronic, Santa Rosa, Calif), can be compared.

Anatomic predictors for late mortality after standard endovascular aneurysm repair.

OBJECTIVE: Abdominal aortic aneurysm (AAA) management involves a decision process that takes into account anatomic characteristics, surgical risks, patients' preferences, and expected survival. Whereas larger AAA diameter has been associated with increased mortality after both standard endovascular aneurysm repair (EVAR) and open repair, it is unclear whether survival after EVAR is influenced by other anatomic characteristics. The purpose of this study was to determine the importance of baseline anatomic features on survival after EVAR. METHODS: All patients treated at a tertiary teaching center with EVAR for intact standard infrarenal AAA from 2000 to 2014 were included. The civil data registry was queried to determine survival status; causes of death were obtained from death certificates. The primary study end point was to determine the impact of baseline morphologic features on all-cause and cardiovascular mortality after EVAR. RESULTS: This study included 404 EVAR patients (12.1% women; mean age, 73 years) with a median follow-up of 5.8 years (interquartile range, 3.1-7.4 years). The 5- and 10-year overall survival rates for the entire population after EVAR were 70% (95% confidence interval [CI], 66%-75%) and 43% (95% CI, 37%-50%), respectively. Only AAA diameter >70 mm (hazard ratio [HR], 1.75; 95% CI, 1.20-3.56) was identified as an independent anatomic predictor of all-cause mortality. Death due to cardiovascular causes occurred in 60 (38.5%) patients. Aneurysm-related mortality was responsible for six of the cardiovascular-related deaths. In multivariable analysis, both neck diameter ≥30 mm (HR, 2.16; 95% CI, 1.05-4.43) and AAA diameter >70 mm (HR, 2.45; 95% CI, 1.34-4.46) were identified as independent morphologic risk factors for cardiovascular mortality, whereas >25% circumferential neck thrombus (HR, 0.32; 95% CI, 0.13-0.77) was protective. CONCLUSIONS: This study suggests that patients with AAA diameters >70 mm are at increased risk of all-cause and cardiovascular mortality. In addition, patients with infrarenal neck diameters ≥30 mm have a greater risk of cardiovascular mortality, although AAA-related deaths were not more frequent in this group of patients. Consequently, a more aggressive management of cardiovascular medical comorbidities may be warranted to improve survival after standard EVAR in these patients.