Assessment of fitness for open repair in patients with infrarenal abdominal aortic aneurysms.

OBJECTIVE: Endovascular aortic repair (EVAR) was originally designed as a treatment modality for patients with abdominal aortic aneurysms (AAAs) deemed unfit for open repair. However, the definition of "unfit for open repair" is largely subjective and heterogenous. The purpose of this study was to compare patients deemed unfit for open repair who underwent EVAR to a matched cohort who underwent open repair for infrarenal AAAs. METHODS: The Vascular Quality Initiative of the Society for Vascular Surgery was queried for patients who underwent EVAR and open infrarenal AAA repair from 2003 to 2022. Patients that underwent EVAR were included if they were deemed unfit for open repair by the operating surgeon. EVAR patients deemed unfit because of a hostile abdomen were excluded. Patients in both the open and EVAR datasets were excluded if their repair was deemed non-elective or if they had prior aortic surgery. EVAR patients were matched to a cohort of open patients. The primary outcome for this study was 1-year mortality. Secondary outcomes included 30-day mortality, major adverse cardiac events, pulmonary complications, non-home discharge, reinterventions, and 5-year survival. RESULTS: A total of 5310 EVAR patients were identified who were deemed unfit for open repair. Of those, 3028 EVAR patients (57.0%) were able to be matched 1:1 to a cohort of open patients. Open patients had higher rates of major adverse cardiac events (20.2% vs 4.4%; P < .001), pulmonary complications (12.8% vs 1.6%; P < .001), non-home discharges (28.5% vs 7.9%; P < .001), and 30-day mortality (4.5% vs 1.4%; P < .001). There were no differences in early survival, but open repair had better middle and late survival compared with EVAR over the course of 5 years. A total of 74 EVAR patients (2.4%) had reinterventions during the study period. EVAR patients that required interventions had higher 1-year (40.5% vs 7.3%; P < .001) and 5-year mortality (43.2% vs 14.1%; P < .001) compared with those that did not require reinterventions. EVAR patients who had reinterventions had higher 1-year (40.5% vs 6.3%; P < .001) and 5-year (43.2% vs 20.3%; P = .006) mortality compared with their matched open cohort. CONCLUSIONS: Patients undergoing EVAR for AAAs who are deemed unfit for open repair have better perioperative morbidity and mortality compared with open repair. However, patients who had an open repair had better middle and late survival over the course of 5 years. The categorization of unfitness for open surgery may be inaccurate and re-evaluation of this terminology/concept should be undertaken.

Reassuring Intraoperative Parameters Do Not Obviate the Need for Infrainguinal Bypass Completion Angiograms.

OBJECTIVE: To determine if routine completion angiography for lower extremity bypasses using vein conduit results in lower rates of postoperative bypass occlusion. SUMMARY OF BACKGROUND DATA: With the increasing availability of on-table angiography and significant advancements in endovascular techniques, some operators routinely perform completion angiograms. The effect of this surgical paradigm has yet to be rigorously compared to the more widespread selective use of completion imaging in the modern era. METHODS: This retrospective cohort study included infrainguinal arterial bypass procedures utilizing vein conduit completed at a single hospital system from 2001 to 2018 and compared postoperative outcomes between bypasses that underwent routine completion angiography versus selective completion angiography. Notably, any bypasses that underwent completion angiography due to intraoperative concerns were excluded from this analysis. RESULTS: 666 bypasses that were performed in 589 patients met inclusion criteria. 126 (16.9%) bypasses were classified into the routine completion angiogram group compared to 540 (81.0%) into the selective completion angiogram group. Patients who underwent routine completion angiograms had a rate of intraoperative reintervention of 22.2%. The routine angiogram group had lower rates of reintervention (3.9% vs 10.0%, P = 0.03) and graft occlusion (2.3% vs 9.2%, P = 0.01) at 1-month postoperatively. CONCLUSION: Lower extremity bypasses using vein conduit that undergo routine completion angiography are associated with lower rates of graft occlusion at 30-days postoperatively. Completion angiography should thus be routinely performed in infrainguinal bypasses that utilize venous conduit.

Longer patient travel distance is associated with increased non-index readmission after complex aortic surgery.

OBJECTIVE: Recently evolving practice patterns in complex aortic surgery have led to regionalization of care within fewer centers in the United States, and thus patients may have to travel farther for complex aortic care. Travel distance has been associated with inferior outcomes after non-vascular surgery, particularly non-index readmission. This study aims to assess the impact of patient travel distance on perioperative outcomes and readmissions after complex aortic surgery. METHODS: A retrospective review was conducted of all patients in the Vascular Quality Initiative and Vascular Implant Surveillance and Interventional Outcomes Network databases undergoing complex endovascular aortic repair (EVAR) including internal iliac or visceral vessel involvement, complex thoracic endovascular aortic repair (TEVAR) including zone 0 to 2 proximal extent or branched devices, and complex open abdominal aortic aneurysm (AAA) repair including suprarenal or higher clamp sites. Travel distance was stratified by rural/urban commuting area (RUCA) population-density category. Wilcoxon and χ2 tests were used to assess relationships between travel distance quintiles and baseline characteristics, mortality, and readmission. Travel distance and other factors were included in multivariable Cox models for survival and Fine-Gray competing risk models for freedom from readmission. RESULTS: Between 2011 and 2018, 8782 patients underwent complex aortic surgery in the Vascular Quality Initiative and Vascular Implant Surveillance and Interventional Outcomes Network databases, including 4822 complex EVARs, 2672 complex TEVARs, and 1288 complex open AAA repairs. Median travel distance was 22.8 miles (interquartile range [IQR], 8.6-54.8 miles). Median age was 75 years for all distance quintiles, but patients traveling longer distances were more likely female (26.8% in quintile 5 [Q5] vs 19.9% in Q1; P < .001), white (93.8% of Q5 vs 83.8% of Q1; P < .001), to have larger-diameter AAAs (median 59 mm for Q5 vs 55 mm for Q1; P < .001), and to have had prior aortic surgery (20.8% for Q5 vs 5.9% for Q1; P < .001). Overall 30-day readmission was more common at farther distances (18.1% for Q5 vs 14.8% for Q1; P = .003), with higher non-index readmission (11.2% for Q5 vs 2.7% for Q1; P < .001) and conversely lower index readmission (6.9% for Q5 vs 12.0% for Q1; P < .001). Multivariable-adjusted Fine-Gray models confirmed greater hazard of non-index readmission with farther distance, with a Q5 hazard ratio of 3.02 (95% confidence interval, 2.12-4.30; P < .001). Multivariable-adjusted Cox models demonstrated no association between travel distance and long-term survival but found that non-index readmission was associated with increased long-term mortality (hazard ratio, 1.46; 95% confidence interval, 1.20-1.78; P = .0001). CONCLUSIONS: Patients traveling farther for complex aortic surgery demonstrate higher non-index readmission, which, in turn, is associated with increased long-term mortality risk. Aortic centers of excellence should consider targeting these patients for more comprehensive follow-up and care coordination to improve outcomes.

Partial and complete explantation of aortic endografts in the modern era.

OBJECTIVE: Despite the progressive advancement of devices for endovascular aortic repair (EVAR), endografts continue to fail, requiring explant. We present a single-institutional experience of EVAR explants, characterizing modern failure modes, presentation, and outcomes for partial and complete EVAR explantation. METHODS: A retrospective analysis was performed of all EVARs explanted at an urban quaternary center from 2001 to 2020, with one infected endograft excluded. Patient and graft characteristics, indications, and perioperative and long-term outcomes were analyzed. Partial versus complete explants were performed per surgeon discretion without a predefined protocol. This process was informed by patient risk factors; asymptomatic, symptomatic, or ruptured aneurysm presentation; and anatomical or intraoperative factors, including endoleak type. RESULTS: From 2001 to 2020, 52 explants met the inclusion and exclusion criteria. More than one-half (57.7%) were explants of EVAR devices placed at outside institutions, designated nonindex explants. Most patients were male (86.5%), the median age was 74 years (interquartile range, 70-78 years). More than one-half (61.5%) were performed in the second decade of the study period. The most commonly explanted grafts were Gore Excluder (n = 9 grafts), Cook Zenith (n = 8), Endologix AFX (n = 7), Medtronic Endurant (n = 5), and Medtronic Talent (n = 5). Most grafts (78.8%) were explanted for neck degeneration or sac expansion. Five were explanted for initial seal failure, five for symptomatic expansion, and seven for rupture. The median implant duration was 4.2 years, although ranging widely (interquartile range, 2.6-5.1 years), but similar between index and nonindex explants (4.2 years vs 4.1 years). Partial explantation was performed in 61.5%, with implant duration slightly lower, 3.2 years versus 4.4 years for complete explants. Partial explantation was more frequent in index explants (68.2% vs 56.7%). The median length of stay was 8 days. The median intensive care unit length of stay was 3 days, without significant differences in nonindex explants (4 days vs 3 days) and partial explants (4 days vs 3 days). Thirty-day mortality occurred in two nonindex explants (one partial and one complete explant). Thirty-day readmission was similar between partial and complete explants (9.7% vs 5.0%), without accounting for nonindex readmissions. Long-term survival was comparable between partial and complete explants in Cox regression (hazard ratio, 2.45; 95% confidence interval, 0.79-7.56; P = .12). CONCLUSIONS: Explants of EVAR devices have increased over time at our institution. Partial explant was performed in more than one-half of cases, per operating surgeon discretion, demonstrating higher blood loss, more frequent acute kidney injury, and longer intensive care unit stays, however with comparable short-term mortality and long-term survival.

Anisotropic nanocluster arrays to a diminished zone: different regimes of surface deposition of gold nanocolloids.

Evaporation-induced assembly of nanoparticles has emerged as a versatile technique for the production of large-scale ordered structures and materials with complex features. In this study, we show that a dried particulate of an anisotropic nanocolloid undergoes non-ubiquitous surface morphological transitions at varying particle concentrations. Below 5 nM, deposits reveal the formation of linear arrays of AuNR clusters outside of the coffee ring and an annular CTAB-rich depletion zone in the inner vicinity of the coffee ring. For nanoparticle concentrations ≥5 nM, the outer cluster deposits disappear and a region of reduced AuNR density, sandwiched between the coffee ring and the depletion zone, analogous to the diminished zone, is observed. Within the coffee-ring deposits, nanoscale smectic AuNR assembly occurs via the expulsion of the cetyltrimethyl ammonium bromide (CTAB) bilayer, which contributes to the inward solutal Marangoni flow. An enhanced inward solutal Marangoni flow at high particle concentrations assists in the formation of a wider depletion zone, the emergence of the diminished zone and suppression of the width of the coffee-ring deposits. Through detailed analysis of data from ex situ (scanning electron microscopy, SEM) and in situ (contact angle and confocal imaging) measurements, we establish a direct correlation between the different evaporation modes and the various deposition regimes. A detailed mechanism for the surface morphology modulation of AuNR deposits by tuning the nanoparticle concentration in the drying sessile drop is discussed.

Ordered stripes to crack patterns in dried particulates of DNA-coated gold colloids via modulating nanoparticle-substrate interactions.

The surface pattern in dried droplets of nanoparticle suspension possesses direct correlation with the evaporation profile, which apart from the bulk parameters, can also be altered by tuning the nanoscale interactions. Here, we show that, for sessile drops of DNA-coated gold nanoparticle (DNA-AuNP) solution, the alteration in evaporation pathway of TPCL (three-phase contact line) from stick-slip to mixed mode leads to a surface morphological transition from concentric rings with stripes to radial crack formation within the coffee ring deposit. A freshly cleaned silicon substrate offers hydrophilic/favorable substrate-nanoparticle interaction and produces multiple ordered stripes due to stick-slip motion of the TPCL. Using a SiO2/Si substrate with ∼200 nm of oxide layer leads to an increase in the initial water contact angle θi-w by ∼40°, due to increased hydrophobicity of the substrate. Three distinct modes of evaporation are observed - constant contact radius (CCR), constant contact angle (CCA) and mixed mode, resulting in the formation of radial cracks on a thick coffee ring structure. The critical thickness (hc), beyond which the cracks start to appear, was measured to be ∼600 nm and is in close agreement with the theoretical estimate of ∼510 nm. Through in situ contact angle and ex situ SEM measurements, we provide an understanding of the observed surface morphological transition in the dried particulate at various nanoparticle densities. Further analysis of the coffee ring width (d), linear crack density (σ) and crack spacing (λ) provides insight into the mechanism of crack formation for droplets dried on oxide-coated substrates.

Greater Patient Travel Distance is Associated with Perioperative and One-Year Cost Increases After Complex Aortic Surgery.

BACKGROUND: With increasing regionalization of complex aortic surgery within fewer US centers, patients may face increased travel burden when accessing aortic surgery. Longer travel distances have been associated with inferior outcomes after major surgery; however, the impacts of distance on reinterventions and costs have not been described. This study aims to assess the association between patient travel distance and longer-term outcomes including costs and reinterventions after complex aortic surgery. METHODS: A retrospective review was conducted of all patients in the Vascular Implant Surveillance and Interventional Outcomes Network database undergoing complex endovascular aortic repair including internal iliac or visceral vessel involvement, complex thoracic endovascular aortic repair including Zone 0-2 proximal extent or branched devices, and complex open abdominal aortic aneurysm repair including suprarenal or higher clamp sites. Travel distance was stratified by Rural-Urban Commuting Area population-density category. Multinomial logistic regression models, negative-binomial models, and zero-inflated Poisson models were used to assess the association between travel distance and index procedural and comprehensive first-year costs, long-term imaging, and long-term reinterventions, respectively. RESULTS: Between 2011 and 2018, 8,782 patients underwent complex aortic surgery in the Vascular Implant Surveillance and Interventional Outcomes Network database, including 4,822 complex endovascular aortic repairs, 2,672 complex thoracic endovascular aortic repairs, and 1,288 complex open abdominal aortic aneurysm repairs. Median travel distance was 22.8 miles (interquartile range 8.6-54.8 miles, range 0-2,688.9 miles). Median age was 75 years for all distance quintiles. Patients traveling farther were more likely to be female (26.8% in quintile 5 [Q5] vs. 19.9% in Q1, P < 0.001) and to have had a prior aortic surgery (20.8% for Q5 vs. 5.9% for Q1, P < 0.001). Patients traveling farther had higher index procedural costs, with adjusted odds ratio (OR) 2.34 (95% confidence interval [CI] 1.86-2.94, P < 0.0001) of being in the highest cost tertile versus lowest for patients in Q5 vs. Q1. For patients with ≥ 1-year follow-up, those traveling farther had higher imaging costs, with adjusted Q5 OR 1.55 (95% CI 1.22-1.95, P = 0.0002), and comprehensive first-year costs, with adjusted Q5 OR 2.06 (95% CI 1.57-2.70, P < 0.0001). In contrast, patients traveling farther had similar numbers of reinterventions and imaging studies postoperatively. CONCLUSIONS: Patients traveling farther for complex aortic surgery have higher procedural costs, postoperative imaging costs, and comprehensive first-year costs. These patients should be targeted for increased care coordination for improved outcomes and healthcare system burden.

Implementation of a Consensus-Driven Quality Improvement Protocol to Decrease Length of Stay after Elective Carotid Endarterectomy.

BACKGROUND: National guidelines stipulate that postoperative length-of-stay (LOS) after elective carotid endarterectomy (CEA) should not exceed 1 day on average, yet perioperative care coordination gaps may limit the ability for institutions to achieve this goal. Internal review determined that increased LOS after CEA at our institution was frequently attributable to urinary retention or postoperative hypertension. We designed and implemented a quality improvement (QI) protocol aiming to better our institutional performance in postoperative LOS after CEA, consisting of 2 Plan-Do-Study-Act (PDSA) cycles. METHODS: In the first PDSA cycle, a division-wide standardized protocol was developed by which antihypertensive medications were managed preoperatively and through postoperative day (POD) 1. This protocol included dedicated patient outreach with instructions for at-home antihypertensive management through the morning of POD 0. Second, alpha-1-blockade was administered to all male patients preoperatively. All patients receiving an elective CEA performed at our institution by vascular surgeons were included in the protocol. The primary outcome measure was defined percent failure of the LOS >1 day metric, with raw LOS as a secondary outcome measure. Process measures included adherence to the antihypertensive medication protocol and adherence to preoperative alpha-1 blockade. Balance measures included documented intraoperative hypotension and 30-day readmission. Fisher's exact test was used to evaluate relationships between preintervention and postintervention cohorts and the outcome measure. Wilcoxon rank-sum tests were used to evaluate relationships between cohorts and total LOS. RESULTS: Baseline performance on the LOS >1 day metric after elective CEA was 58.3% in the 8 months prior to intervention, across 48 patients. Both PDSA interventions were implemented simultaneously. In the 12 months after intervention, 64 patients met protocol inclusion criteria, including 19 symptomatic patients (29.7%). Process measure success for preoperative antihypertensive regimen adherence was 89.8%. For males not chronically prescribed alpha-1 blockade preoperatively, process measure success for adherence to preoperative alpha-1 blockade was 78.8%. The intraoperative hypotension balance measure occurred in 1 patient (1.6%). Performance on the LOS >1 day outcome measure was improved to 32.8% (P = 0.01). Performance on the raw LOS outcome measure was similar between the preintervention cohort (median 2 days, interquartile range [IQR] 1-2) and postintervention cohort (median 1 day, IQR 1-2, P = 0.07). Performance on the 30-day readmission balance measure was similar between preintervention (6.3%) and postintervention cohorts (9.4%, P = 0.73). CONCLUSIONS: The consensus-driven development and implementation of a QI protocol to reduce postoperative LOS after CEA showed promising results in our institution, with approximately 40% improvement in the primary outcome measure. Wider efforts to improve LOS after CEA should include a focus on minimization of postoperative hypertension and urinary retention.

Routine Completion Angiography for Infrainguinal Bypasses Using Prosthetic Conduit: No Effect on Postoperative Patency.

BACKGROUND: Recent studies have demonstrated increased postoperative patency with the use of routine completion angiography for bypass using venous conduit. Compared to vein conduits, however, prosthetic conduits are less plagued by technical issues such as unlysed valves or arteriovenous fistulae. The effect of routine completion angiography on bypass patency in prosthetic bypasses has yet to be compared to the more traditional selective use of completion imaging. METHODS: A retrospective review of all infrainguinal bypass procedures using prosthetic conduit completed at a single hospital system from 2001 to 2018 was performed. Demographics, comorbidities, intraoperative reintervention rates, and 30-day rates of graft thrombosis were analyzed. Statistical analysis included t-tests, chi-square tests, and cox regression. RESULTS: Four hundred and ninety-eight bypasses that were performed in 426 patients met inclusion criteria. Fifty-six (11.2%) bypasses were classified into the routine completion angiogram group compared to 442 (88.8%) into the no completion angiogram group. Patients who underwent routine completion angiograms had a rate of intraoperative reintervention of 21.4%. When comparing bypasses that underwent routine completion angiography versus no completion angiography, there were no significant differences in rates of reintervention (3.5% vs. 4.5%, P = 0.74) or graft occlusion (3.5% vs. 4.7%, P = 0.69) at 30-days postoperatively. CONCLUSIONS: Almost one-quarter of lower extremity bypasses using prosthetic conduit that undergo routine completion angiography undergo postangiogram bypass revision; however, this is not associated with an increased graft patency at 30 days postoperatively.

Increased anti-thrombotic therapy is associated with decreased major adverse limb events in patients with low wound and foot infection scores.

INTRODUCTION: The optimal anti-thrombotic management of patients after lower extremity bypass has yet to be fully elucidated, in part due to significant heterogeneity in patient presentation and practice patterns. The Wound, Ischemia, and foot Infection (WIfI) score is a validated scoring system to assist in the management of patients with chronic limb threatening ischemia (CLTI). We hypothesized that performing a restriction analysis based on WIFI scores would assist in the postoperative anti-thrombotic management of patients undergoing infrainguinal bypass. METHODS: A retrospective cohort of infrainguinal bypass procedures completed at a single hospital system between January 2018 and January 2021 was selected, and preoperative WIfI scores were extracted for each patient. Patients with either Wound scores of 2 and 3, or Ischemia Scores of 0 and 1, or Foot Infection Scores of 3 were excluded. Based on the type of anti-thrombotic regimen on discharge, demographics, comorbidities, type of bypass, 30-day rates of graft occlusion, major amputation, mortality, and major adverse limb events (MALE) were analyzed. Statistical analysis included t-tests, chi square tests, and time-to-event survival analysis. RESULTS: 230 procedures were included in the study. 69 (30.0%) patients were discharged on single antiplatelet therapy (SAPT), compared to 161 (70.0%) who were discharged on either dual antiplatelet therapy or anticoagulation (DAPT/AC). There was a higher prevalence of bypasses using prosthetic conduit in the DAPT/AC group (45.9 vs 31.8%, p = .047); no other demographic or procedural variable analyzed had any significant differences. At 30-days postoperatively, there was no significant difference in postoperative reintervention rates, however, the DAPT/AC group had significantly lower rates of mortality (1.2 vs 7.2%, p = .01), major amputation (1.2% vs 5.8%, p = .04), and MALE (3.7 vs 13.0%, p < .01). There were no significant differences in bleeding complications. Survival analysis demonstrated that MALE-free survival was higher in the DAPT/AC group compared to the SAPT group (p < .01). On Cox regression analysis, DAPT/AC was associated with significantly decreased rates of MALE + mortality (Hazard Ratio (HR) 0.20 [0.06 - 0.66]). CONCLUSION: Lower extremity bypasses patients with low Wound and low foot Infection scores who are discharged on DAPT/AC postoperatively have a significantly higher 30-day MALE-free survival rate compared to patients discharged on SAPT; consideration could be made to preferentially discharge such post-bypass patients on DAPT/AC.

Trends in Female Authorship in High Impact Surgical Journals Between 2008 and 2018.

OBJECTIVE: This study evaluates the distribution of authorship by sex over the last 10 years among the top 25 surgical journals. SUMMARY OF BACKGROUND DATA: Despite an increase in women entering surgical residency, there remains a sex disparity in surgical leadership. Scholarly activity is the foundation for academic promotion. However, few studies have evaluated productivity by sex in surgical literature. METHODS: Original research in the 25 highest-impact general surgery/subspecialty journals were included (1/2008-5/2018). Journals with <70% identified author sex were excluded. Articles were categorized by sex of first, last, and overall authorship. We examined changes in proportions of female first, last, and overall authorship over time, and analyzed the correlation between these measurements and journal impact factor. RESULTS: There were 71,867 articles from 19 journals included. Sex was successfully predicted for 87.3% of authors (79.1%-92.5%). There were significant increases in the overall percentage of female authors (ß = 0.55, P < 0.001), female first authors (ß = 0.97, P < 0.001), and female last authors (ß = 0.53, P < 0.001) over the study period. Notably, all cardiothoracic subspecialty journals did not significantly increase the proportion of female last authors over the study period. There were no correlations between journal impact factor and percentage of overall female authors (rs = 0.39, P = 0.09), female first authors (rs = 0.29, P = 0.22), or female last author (rs = 0.35, P = 0.13). CONCLUSIONS: This study identifies continued but slow improvement in female authorship of high-impact surgical journals during the contemporary era. However, the improvement was more apparent in the first compared to senior author positions.

Structural and Dynamical Studies of a Lipid-Nanoclay Composite Layer at the Air-Water Interface.

We modulate the adsorption affinities of nanoclay particles for the air-water interface by changing the cationic surface charge composition of the lipid monolayer and thereby tune the attractive electrostatic interaction between the positively charged lipid layer and the zwitterionic nanoclay particles in the water subphase. Our findings emphasize the significance of electrostatic interaction between lipids and the nanoclay, as well as its impact on the structural and viscoelastic features of the composite layer. We use surface pressure (Π)-mean molecular area (A) isotherms, atomic force microscope (AFM), Brewster angle microscopy (BAM), and energy dispersive X-ray spectrsocopy (EDXS) measurements to analyze the structure phases of lipid and lipid-nanoclay composite interfacial layer. The Π-A isotherm curve shows that the lipid-nanoclay composite layer has a larger lift-off area than the neat lipid layer, indicating that nanoparticles adsorb at the lipid layer via electrostatic interaction between lipid and nanoclay molecules. The surface density of the adsorbed nanoclay particles increases with an increase in the composition of the cationic lipid molecules. The stress relaxation response of the composite layer, measured using step compression measurements, exhibits exponential decay and ubiquitous dependence on the cationic dimyristoy-trimethylammonium propane (DMTAP) composition in the lipid layer with crossover to faster relaxation dynamics at DMTAP > 0.75. The power-law study of the frequency-dependent dynamic viscoelastic responses of the interfacial layer, measured using the barrier oscillation method, reveals a transition from glass-like response from neat lipid layer to gel-like dynamic response for the lipid-nanoclay composite layer. A solid-like behavior is evident for all the interface layers with dilation elastic modulus (E') > dilational viscous modulus (E″); however, the dynamic response of the neat layer is largely frequency-independent, whereas lipid-nanoclay composite layers with DMTAP > 0.75 reveal a frequency-dependent dynamic responses. The frequency-dependent power-law exponent of E', E″ increases on increasing the fractional composition of cationic DMTAP from 0.1 to 1.0, which forms a saturated interface of laponite particles and behaves as a viscoelastic gel in 2D.

Effect of mono- and multi-valent ionic environments on the in-lattice nanoparticle-grafted single-stranded DNA.

Polyelectrolyte (PE) chains respond in a complex manner to multivalent salt environments, and this behavior depends on pH, temperature, and the presence of specific counter ions. Although much work has been done to understand the behaviour of free PE chains, it is important to reveal their behaviour on a nanoparticle's surface, where surface constraints, particle geometry, and multi-chain environment can affect their behaviour and contribute to particles' assembly states. Our work investigates, using in situ small-angle X-ray scattering (SAXS), the morphology of PE (single-stranded DNA) chains grafted onto the surface of spherical gold nanoparticles assembled in a lattice in the presence of monovalent, divalent and trivalent salts. For divalent salts, the DNA brush length was found to decrease at a faster rate with salt concentration than in the monovalent salt environment, while trivalent salts led to chain collapse. Using a power law analysis and the modified Daoud-Cotton model, we have obtained insight into the mechanism of a nanoparticle-grafted chain's response to ionic environments. Our analysis suggests that the decrease in brush length is due to the conventional electrostatic screening for monovalent systems, whereas for divalent systems both electrostatic screening and divalent ion bridging must be considered.

Tuning the properties of graphene quantum dots by passivation.

The electronic and optical properties of graphene quantum dots (GQDs) of size less than 10 nm are different from those of graphene sheets due to quantum confinement effects. For analyzing their use in optoelectronic applications, it is very crucial to optimally tune the bandgap and engineer the controlling parameters. In the present work, a systematic investigation of the band gap of hexagonal GQDs has been carried out by examining their HOMO and LUMO energies. Passivation of dangling bonds of these GQDs has been carried out with the help of electron-withdrawing substituents in order to tune the band gap and engineer their optical properties such as absorption and emission spectra by carrying out the simulation with Density Functional Theory formalism using Gaussian 09 software. Carrying out passivation with electronegative element fluorine (F) effectively decreases the band gap of these QDs resulting in a redshift in the absorption spectra. The HOMO and LUMO topographical surfaces have been used to understand the absorption spectra. These surfaces show some σ-bond characteristics along with π-bond properties on passivating GQDs with the F-atom which further results in alteration of their energies and a corresponding decrease in their band gap. Here, the absorption is found to be dependent on the size of GQDs and the type of passivating atoms (H or F). The results thus obtained are found to be in good consonance with those reported in the literature engaging different methods. The present analysis may prove to be useful in improving the working of solar cells and other optoelectronic devices.

Photocatalytic properties of anisotropic ß-PtX2 (X = S, Se) and Janus ß-PtSSe monolayers.

The highly efficient photocatalytic water splitting process to produce clean energy requires novel semiconductor materials to achieve a high solar-to-hydrogen energy conversion efficiency. Herein, the photocatalytic properties of anisotropic ß-PtX2 (X = S, Se) and Janus ß-PtSSe monolayers were investigated based on the density functional theory. The small cleavage energy for ß-PtS2 (0.44 J m-2) and ß-PtSe2 (0.40 J m-2) endorses the possibility of mechanical exfoliation from their respective layered bulk materials. The calculated results revealed that the ß-PtX2 monolayers have an appropriate bandgap (∼1.8-2.6 eV) enclosing the water redox potential, light absorption coefficient (∼104 cm-1), and exciton binding energy (∼0.5-0.7 eV), which facilitates excellent visible-light-driven photocatalytic performance. Remarkably, the inherent structural anisotropy leads to an anisotropic high carrier mobility (up to ∼5 × 103 cm2 V-1 S-1), leading to a fast transport of photogenerated carriers. Notably, the required small external potential to realize hydrogen evolution reaction and oxygen evolution reaction processes with an excellent solar-to-hydrogen energy conversion efficiency for ß-PtSe2 (∼16%) and ß-PtSSe (∼18%) makes them promising candidates for solar water splitting applications.

Novel phosphorus-based 2D allotropes with ultra-high mobility.

Electronic structure calculations based on density functional theory were performed to investigate structural, mechanical, and electronic properties of phosphorene-based large honeycomb dumbbell (LHD) hybrid structures and a new phosphorene allotrope, referred to as ψ″-P. The LHD hybrids (i.e., X6P4; X being C or Si or Ge or Sn) and ψ″-P have significantly higher bandgaps than the corresponding pristine LHD structures, except the case of C6P4, which is metallic. ψ″-P is found to be a highly flexible p-type material which shows strain-engineered photocatalytic activity in a highly alkaline medium. The carrier mobility of the considered systems is as high as 105 cm2 V-1 s-1 (specifically the electron mobility of LHD structures). The calculated STM images display the surface morphologies of the LHD hybrids and ψ″-P. The predicted phosphorus-based 2D structures with novel electronic properties may be candidate materials for nanoscale devices.

Liquid interfaces with pH-switchable nanoparticle arrays.

Stimuli-responsive 2D nanoscale systems offer intriguing opportunities for creating switchable interfaces. At liquid interfaces, such systems can provide control over interfacial energies, surface structure, and rheological and transport characteristics, which is relevant, for example, to bio- and chemical reactors, microfluidic devices, and soft robotics. Here, we explore the formation of a pH-responsive membrane formed from gold nanoparticles grafted with DNA (DNA-NPs) at a liquid-vapor interface. A DNA-NP 2D hexagonal lattice can be reversibly switched by pH modulation between an expanded state of non-connected nanoparticles at neutral pH and a contracted state of linked nanoparticles at acidic pH due to the AH+-H+A base pairing between A-motifs. Our in situ surface X-ray scattering studies reveal that the reversible lattice contraction can be tuned by the length of pH-activated linkers, with up to ∼71% change in surface area.

Stability and carrier transport properties of phosphorene-based polymorphic nanoribbons.

Few-layer black phosphorene has recently attracted significant interest in the scientific community. In this paper, we consider several polymorphs of phosphorene nanoribbons (PNRs) and employ deformation potential theory within the effective mass approximation, together with density functional theory, to investigate their structural, mechanical and electronic properties. The results show that the stability of a PNR strongly depends on the direction along which it can be cut from its 2D counterpart. PNRs also exhibit a wide range of line stiffnesses ranging from 6 × 1010 eV m-1 to 18 × 1011 eV m-1, which has little dependence on the edge passivation. Likewise, the calculated electronic properties of PNRs show them to be either a narrow-gap semiconductor (E g < 1 eV) or a wide-gap semiconductor (E g > 1 eV). The carrier mobility of PNRs is found to be comparable to that of black phosphorene. Some of the PNRs show an n-type (p-type) semiconducting character owing to their higher electron (hole) mobility. Passivation of the edges leads to n-type â†” p-type transition in many of the PNRs considered. The predicted novel characteristics of PNRs, with a wide range of mechanical and electronic properties, make them potentially suitable for use in nanoscale devices.