Scalable Ab Initio Electronic Structure Methods with Near Chemical Accuracy for Main Group Chemistry.

This study evaluates the precision of widely recognized quantum chemical methodologies, CCSD(T), DLPNO-CCSD(T), and localized ph-AFQMC, for determining the thermochemistry of main group elements. DLPNO-CCSD(T) and localized ph-AFQMC, which offer greater scalability compared to canonical CCSD(T), have emerged over the past decade as pivotal in producing precise benchmark chemical data. Our investigation includes closed-shell, neutral molecules, focusing on their heat of formation and atomization energy sourced from four specific small molecule data sets. First, we selected molecules from the G2 and G3 data sets, noted for their reliable experimental heat of formation data. Additionally, we incorporate molecules from the W4-11 and W4-17 sets, which provide high-level theoretical reference values for atomization energy at 0 K. Our findings reveal that both DLPNO-CCSD(T) and ph-AFQMC methods are capable of achieving a root-mean-square deviation of less than 1 kcal/mol across the combined data set, aligning with the threshold for chemical accuracy. Moreover, we make efforts to confine the maximum deviations within 2 kcal/mol, a degree of precision that significantly broadens the applicability of these methods in fields such as biology and materials science.

Comparative Evaluation of Microbial Flora of Endodontic Origin in Teeth with Endo-Perio Lesions.

Background: Endodontic microbial flora plays a pivotal role in the development and persistence of periodontal endodontic lesions (PELs). Understanding the composition and prevalence of microbial species in PELs is essential for effective treatment strategies. Materials and Methods: Microbial samples were collected from 50 teeth diagnosed with PELs. Sterile paper points were used to obtain samples from the root canals. Deoxyribonucleic acid (DNA) was extracted and subjected to polymerase chain reaction (PCR) amplification of the 16S ribosomal RNA (rRNA) gene to identify bacterial species. The obtained data were analyzed using statistical methods. Results: The microbial analysis revealed a diverse range of bacterial species in PELs. The most prevalent species were Porphyromonas gingivalis (32.5%), Treponema denticola (28.0%), and Fusobacterium nucleatum (22.5%). Streptococcus mutans (9.0%) and Actinomyces naeslundii (8.0%) were also frequently detected. Additionally, Prevotella intermedia (7.0%), Aggregatibacter actinomycetemcomitans (3.5%), and Enterococcus faecalis (2.5%) were present in lower frequencies. Conclusion: The presence of a diverse microbial flora in teeth with PELs underscores the polymicrobial nature of these lesions. The predominance of periodontal pathogens such as Porphyromonas gingivalis, Treponema denticola, and Fusobacterium nucleatum suggests a strong association between periodontal and endodontic infections. A comprehensive understanding of the microbial profile in PELs is crucial for tailored therapeutic approaches targeting the specific pathogens involved.

Toward Linear Scaling Auxiliary-Field Quantum Monte Carlo with Local Natural Orbitals.

We develop a local correlation variant of auxiliary-field quantum Monte Carlo (AFQMC) based on local natural orbitals (LNO-AFQMC). In LNO-AFQMC, independent AFQMC calculations are performed for each localized occupied orbital using a truncated set of tailored orbitals. Because the size of this space does not grow with the system size for a target accuracy, the method has linear scaling. Applying LNO-AFQMC to molecular problems containing a few hundred to a thousand orbitals, we demonstrate convergence of total energies with significantly reduced costs. The savings are more significant for larger systems and larger basis sets. However, even for our smallest system studied, we find that LNO-AFQMC is cheaper than canonical AFQMC, in contrast with many other reduced-scaling methods. Perhaps most significantly, we show that energy differences converge much more quickly than total energies, making the method ideal for applications in chemistry and material science. Our work paves the way for linear scaling AFQMC calculations of strongly correlated systems, which would have a transformative effect on ab initio quantum chemistry.

Response properties in phaseless auxiliary field quantum Monte Carlo.

We present a method for calculating first-order response properties in phaseless auxiliary field quantum Monte Carlo by applying automatic differentiation (AD). Biases and statistical efficiency of the resulting estimators are discussed. Our approach demonstrates that AD enables the calculation of reduced density matrices with the same computational cost scaling per sample as energy calculations, accompanied by a cost prefactor of less than four in our numerical calculations. We investigate the role of self-consistency and trial orbital choice in property calculations. We find that orbitals obtained using density functional theory perform well for the dipole moments of selected molecules compared to those optimized self-consistently.

Evaluation of visual pedagogy teaching method for improving oral hygiene practice in children with Autism: An interventional study.

BACKGROUND: Evaluation of visual pedagogy teaching method for improving oral hygiene practice in children with Autism: An interventional study: Visual pedagogy is a relatively newer approach to improve dental care in autistic children. The present study aimed to evaluate visual pedagogy in the practice of oral hygiene in autistic children. MATERIALS AND METHODS: This interventional and prospective study was conducted in the Department of Paediatric and Preventive Dentistry. Required approval was obtained from Institutional Ethical Board. Written informed consent was obtained from parents/caregivers. The age range was 5-12 years which included 100 participants (40 males and 60 females). Improvement of oral hygiene was evaluated by recording the tooth brushing technique and ability to follow instructions as presented in the educational video shown on smartphones with Wi-Fi/mobile data. Inclusion criteria: (1) Accessibility and (2) Age range between 5 to 12 years. Exclusion criteria: (1) Non-cooperative children, (2) Children receiving medicines that influence oral health, and (3) Inability to follow-ups. Fones technique was used for brushing teeth in video recording demonstrating it in simple structured steps. Statistical analysis was performed using Chi-square and Independent t tests. RESULTS: Statistically significant improvement was observed in oral hygiene (plaque index) after training patients with visual pedagogy. CONCLUSION: In the present study, the use of visual pedagogy showed improvement in the oral hygiene scores of autistic children.

External irrigation of a non-irrigated ablation catheter for effective AV node ablation during conduction system pacing.

Ablation using non-irrigated catheter can lead to rapid rise in temperature of electrode tissue interface from tissue desiccation, steam and coagulum formation and this may limit power delivery and lesion size. We present a novel technique of external irrigation through the long sheath while using a non-irrigated ablation catheter during AV Node ablation and conduction system pacing. By bringing the long sheath closer to the tip of non-irrigated catheter and injecting cold normal saline allows cooling of electrode tissue interface leading to increase in power delivery resulting in a deeper lesion.

Cost-effective Whole Exome Sequencing discovers pathogenic variant causing Neurofibromatosis type 1 in a family from Jammu and Kashmir, India.

Neurofibromatosis type 1 (NF1) is a multisystemic hereditary disorder associated with an increased risk of benign and malignant tumor formation predominantly on the skin, bone, and peripheral nervous system. It has been reported that out of all the NF1 cases, more than 95% cases develop the disease due to heterozygous loss-of-function variants in Neurofibromin (NF1) gene. However, identification of NF1 causative variants by presently recommended method of gene-targeted Sanger sequencing is challenging and cost-intensive due to the large size of the NF1gene with 60 exons spanning about 350 kb. Further, conducting the genetic studies is difficult in low resource regions and among families with the limited financial capabilities, restricting them from availing diagnostic as well as proper disease management measures. Here, we studied a three-generation family from Jammu and Kashmir state in India, with multiple affected family members showing clinical indications of NF1. We combinedly used two applications, Whole Exome Sequencing (WES) and Sanger sequencing, for this study and discovered a nonsense variant NM_000267.3:c.2041C>T (NP_000258.1:p.Arg681Ter*) in exon 18 of NF1 gene in a cost effective manner. In silico analyses further substantiated the pathogenicity of this novel variant. The study also emphasized on the role of Next Generation Sequencing (NGS) as a cost-effective method for the discovery of pathogenic variants in disorders with known phenotypes found in large sized candidate genes. The current study is the first study based on the genetic characterization of NF1 from Jammu and Kashmir-India, highlighting the importance of the described methodology adopted for the identification and understanding of the disease in low resource region. The early diagnosis of genetic disorders would open the door to appropriate genetic counseling, reducing the disease burden in the affected families and the general population at large.

Microscopic Theory of Multimode Polariton Dispersion in Multilayered Materials.

We develop a microscopic theory for the multimode polariton dispersion in materials coupled to cavity radiation modes. Starting from a microscopic light-matter Hamiltonian, we devise a general strategy for obtaining simple matrix models of polariton dispersion curves based on the structure and spatial location of multilayered 2D materials inside the optical cavity. Our theory exposes the connections between seemingly distinct models that have been employed in the literature and resolves an ambiguity that has arisen concerning the experimental description of the polaritonic band structure. We demonstrate the applicability of our theoretical formalism by fabricating various geometries of multilayered perovskite materials coupled to cavities and demonstrating that our theoretical predictions agree with the experimental results presented here.

ipie: A Python-Based Auxiliary-Field Quantum Monte Carlo Program with Flexibility and Efficiency on CPUs and GPUs.

We report the development of a python-based auxiliary-field quantum Monte Carlo (AFQMC) program, ipie, with preliminary timing benchmarks and new AFQMC results on the isomerization of [Cu2O2]2+. We demonstrate how implementations for both central and graphical processing units (CPUs and GPUs) are achieved in ipie. We show an interface of ipie with PySCF as well as a straightforward template for adding new estimators to ipie. Our timing benchmarks against other C++ codes, QMCPACK and Dice, suggest that ipie is faster or similarly performing for all chemical systems considered on both CPUs and GPUs. Our results on [Cu2O2]2+ using selected configuration interaction trials show that it is possible to converge the ph-AFQMC isomerization energy between bis(µ-oxo) and µ-η2:η2 peroxo configurations to the exact known results for small basis sets with 105-106 determinants. We also report the isomerization energy with a quadruple-zeta basis set with an estimated error less than a kcal/mol, which involved 52 electrons and 290 orbitals with 106 determinants in the trial wave function. These results highlight the utility of ph-AFQMC and ipie for systems with modest strong correlation and large-scale dynamic correlation.

Selected configuration interaction wave functions in phaseless auxiliary field quantum Monte Carlo.

We present efficient algorithms for using selected configuration interaction (sCI) trial wave functions in phaseless auxiliary field quantum Monte Carlo (ph-AFQMC). These advances, geared toward optimizing computational performance for longer configuration interaction expansions, allow us to use up to a million configurations in the trial state for ph-AFQMC. In one example, we found the cost of ph-AFQMC per sample to increase only by a factor of about 3 for a calculation with 104 configurations compared to that with a single one, demonstrating the tiny computational overhead due to a longer expansion. This favorable scaling allows us to study the systematic convergence of the phaseless bias in auxiliary field quantum Monte Carlo calculations with an increasing number of configurations and provides a means to gauge the accuracy of ph-AFQMC with other trial states. We also show how the scalability issues of sCI trial states for large system sizes could be mitigated by restricting them to a moderately sized orbital active space and leveraging the near-cancellation of out of active space phaseless errors.

Clinical management of deep osseous defects in cases of peri-implantitis among indian patients.

Peri-implantitis is recognized as a complex pathology which could be defined as infectious inflammatory lesions that usually develop in the tissues around the implants. There are many protocols for the effective management of peri-implantitis that include mechanical debridement, the use of antiseptics and local/systemic antibiotics, and access and regenerative surgery formulated for the treatment of peri-implantitis. This study aims to evaluate the clinical outcomes of a mixed protocol for the regeneration of deep osseous defects. Records obtained from 27 patients who had already received treatment for peri-implantitis on one or more implants were retrospectively examined within the proposed time period between 24 and 30 months after their surgical treatment. A total of 33 implant sites were included and examined retrospectively. Descriptive statistics were calculated that include mean, SD, medians and confidence intervals at 95%. At the baseline, the mean Probing Depth was 8.19 ± 1.23 mm; Bleeding on Probing (BOP) was present on 29 out of 33 treated areas; pus was instead present on 17 out of 33 sites. At the time of final examinations, BOP was present on 9 out of 33 sites; pus was present only on two surgical sites. To conclude, a combined chemical-mechanical and regenerative decontamination therapy is effective in the treatment of peri-implantitis. Further investigation, which includes a control group and/or histologic findings, might be needed to ascertain the clinical results reported in the clinical studies.

Hepatic artery pseudo-aneurysm rupturing into hepato-gastric fistula, a rare cause of massive upper gastrointestinal hemorrhage: Case report.

Hepatic artery pseudo-aneurysm and hepato-fastric fistula are extremely rare clinical entities, which can be caused as complications of amoebic liver abscess. Herein, we report a 45- year old man, who presented with history of hematemesis since last 1 day, melena since last 3 days and fever since last 5 days. On physical examination, he was hemodynamically stable, pallor was noted. Abdominal examination revealed tenderness over the right-upper quadrant. Per-rectal examination showed evidences of melena. Esophagogastroduodenoscopy revealed stomach communicating anteriorly with the abscess cavity from the surrounding, possibly from liver. There was no evidence of fresh bleed during the procedure. The abscess was drained and sent for microbiological evaluation. Computed tomographic angiography revealed a well defined saccular outpouching arising from common hepatic artery with surrounding ill-defined hypodensity around segment V and IVb of liver. Patient underwent transfemoral endovascular coil embolization. Post embolisation, DSA showed complete occlusion of pseudo-aneurysm. He was discharged on oral metronidazole and was doing well on 8-month follow-up with no episodes of rebleed.

Coronary Venous Visualization During Deep Septal Lead Placement: An Unexpected Finding.

Left bundle branch area pacing has emerged as a safe and feasible alternative to conventional pacing. Acute septal injury, septal perforation, and arteriovenous fistula are potential risks of deep septal implants. Contrast drainage through the lesser cardiac veins and subsequent filling of major epicardial vessels may be benign observations noted during forceful hand injection. (Level of Difficulty: Advanced.).

Taming the Sign Problem in Auxiliary-Field Quantum Monte Carlo Using Accurate Wave Functions.

We explore different ways of incorporating accurate trial wave functions into free projection auxiliary-field quantum Monte Carlo (fp-AFQMC). States employed include coupled-cluster singles and doubles, multi-Slater, and symmetry-projected mean-field wave functions. We adapt a recently proposed fast multi-Slater local energy evaluation algorithm for fp-AFQMC, making the use of long expansions from selected configuration interaction methods feasible. We demonstrate how these wave functions serve to mitigate the sign problem and accelerate convergence in quantum chemical problems, allowing the application of fp-AFQMC to systems of substantial sizes. Our calculations on the widely studied model Cu2O22+ system show that many previously reported isomerization energies differ substantially from the near-exact fp-AFQMC value.

Is the right ventricular function affected by permanent pacemaker?

AIMS: The effect of right ventricular (RV) pacing on left ventricular (LV) function has been extensively evaluated, but the effect on RV function per se has not been evaluated systematically. We aimed to assess the effect of dual chamber pacemaker on RV function. METHODS AND RESULTS: All consecutive patients undergoing dual chamber pacemaker from January 2018 to March 2019 for AV block with a structurally normal heart were included. They underwent pre-procedure detailed echocardiography (including three-dimensional [3D] RV ejection fraction [RVEF]), a screening echocardiogram 2 days after pacemaker implantation and again a detailed echocardiogram at 6-month follow-up. We compared the baseline echocardiographic RV parameters with those 6 months after the pacemaker implantation. A total of 60 patients underwent successful pacemaker implantation. At 6 months, most of the patients were pacemaker dependent with pacing percentage of 98.9% ± 2.4%; there was a significant increase in TR and a mean drop in RVEF by 2.8 ± 5%, with 23 (38.3%) having at least a 5% decrease in RVEF. The drop in RVEF positively correlated with TR vena contracta at 6 months but did not correlate with pulmonary artery systolic pressure at 6 months. CONCLUSION: Our study shows the presence of demonstrable RV dysfunction as early as 6 months in a majority of patients who have undergone pacemaker implantation.

Characteristics and resolution of hypertension in obese African American bariatric cohort.

Weight reduction continues to be first-line therapy in the treatment of hypertension (HTN). However, the long-term effect of bariatric malabsorptive surgical techniques such as Roux-en-Y Gastric Bypass (RYGB) surgery in the management of hypertension (HTN) is less clear. African Americans (AA) are disproportionately affected by obesity and hypertension and have inconsistent outcomes after bariatric surgery (BS). Despite a plethora of bariatric literature, data about characteristics of a predominantly AA bariatric hypertensive cohort including hypertension in obese (HIO) are scarce and underreported. The aims of this study were, (1) to describe the preoperative clinical characteristics of HIO with respect to HTN status and age, and (2) to identify predictors of HTN resolution one year after RYGB surgery in an AA bariatric cohort enrolled at the Howard University Center for Wellness and Weight Loss Surgery (HUCWWS). In the review of 169 AA bariatric patients, the average BMI was 48.50 kg/m2 and the average age was 43.86 years. Obese hypertensive patients were older (46 years vs. 37.89 years; p < .0001); had higher prevalence of diabetes mellitus (DM, 43.09% vs. 10.87%; p < .0001) and dyslipidemia (38.2% vs. 13.04%; p 0.002). Hypertensive AA who were taking ≥ 2 antihypertensive medications prior to RYGB were 18 times less likely to experience HTN resolution compared to hypertensive AA taking 0-1 medications, who showed full or partial response. Also, HIO was less likely to resolve after RYGB surgery in patients who needed ≥ 2 antihypertensive medications prior to surgical intervention.