Advanced feature learning and classification of microscopic breast abnormalities using a robust deep transfer learning technique.

Breast cancer is a major health threat, with early detection crucial for improving cure and survival rates. Current systems rely on imaging technology, but digital pathology and computerized analysis can enhance accuracy, reduce false predictions, and improve medical care for breast cancer patients. The study explores the challenges in identifying benign and malignant breast cancer lesions using microscopic image datasets. It introduces a low-dimensional multiple-channel feature-based method for breast cancer microscopic image recognition, overcoming limitations in feature utilization and computational complexity. The method uses RGB channels for image processing and extracts features using level co-occurrence matrix, wavelet, Gabor, and histogram of oriented gradient. This approach aims to improve diagnostic efficiency and accuracy in breast cancer treatment. The core of our method is the SqE-DDConvNet algorithm, which utilizes a 3 × 1 convolution kernel, SqE-DenseNet module, bilinear interpolation, and global average pooling to enhance recognition accuracy and training efficiency. Additionally, we incorporate transfer learning with pre-trained models, including mVVGNet16, EfficientNetV2B3, ResNet101V2, and CN2XNet, preserving spatial information and achieving higher accuracy under varying magnification conditions. The method achieves higher accuracy compared to baseline models, including texture and deep semantic features. This deep learning-based methodology contributes to more accurate image classification and unique image recognition in breast cancer microscopic images. RESEARCH HIGHLIGHTS: Introduces a low-dimensional multiple-channel feature-based method for breast cancer microscopic image recognition. Uses RGB channels for image processing and extracts features using level co-occurrence matrix, wavelet, Gabor, and histogram of oriented gradient. Employs the SqE-DDConvNet algorithm for enhanced recognition accuracy and training efficiency. Transfer learning with pre-trained models preserves spatial information and achieves higher accuracy under varying magnification conditions. Evaluates predictive efficacy of transfer learning paradigms within microscopic analysis. Utilizes CNN-based pre-trained algorithms to enhance network performance.

In-silico analysis and transformation of OsMYB48 transcription factor driven by CaMV35S promoter in model plant - Nicotiana tabacum L. conferring abiotic stress tolerance.

Global crop yield has been affected by a number of abiotic stresses. Heat, salinity, and drought stress are at the top of the list as serious environmental growth-limiting factors. To enhance crop productivity, molecular approaches have been used to determine the key regulators affecting stress-related phenomena. MYB transcription factors (TF) have been reported as one of the promising defensive proteins against the unfavorable conditions that plants must face. Different roles of MYB TFs have been suggested such as regulation of cellular growth and differentiation, hormonal signaling, mediating abiotic stress responses, etc. To gain significant insights, a comprehensive in-silico analysis of OsMYB TF was carried out in comparison with 21 dicot MYB TFs and 10 monocot MYB TFs. Their chromosomal location, gene structure, protein domain, and motifs were analyzed. The phylogenetic relationship was also studied, which resulted in the classification of proteins into four basic groups: groups A, B, C, and D. The protein motif analysis identified several conserved sequences responsible for cellular activities. The gene structure analysis suggested that proteins that were present in the same class, showed similar intron-exon structures. Promoter analysis revealed major cis-acting elements that were found to be responsible for hormonal signaling and initiating a response to abiotic stress and light-induced mechanisms. The transformation of OsMYB TF into tobacco was carried out using the Agrobacterium-mediated transformation method, to further analyze the expression level of a gene in different plant parts, under stress conditions. To summarize, the current studies shed light on the evolution and role of OsMYB TF in plants. Future investigations should focus on elucidating the functional roles of MYB transcription factors in abiotic stress tolerance through targeted genetic modification and CRISPR/Cas9-mediated genome editing. The application of omics approaches and systems biology will be indispensable in delineating the regulatory networks orchestrated by MYB TFs, facilitating the development of crop genotypes with enhanced resilience to environmental stressors. Rigorous field validation of these genetically engineered or edited crops is imperative to ascertain their utility in promoting sustainable agricultural practices.

Predicting current and future habitat of Indian pangolin (Manis crassicaudata) under climate change.

Climate change is among the greatest drivers of biodiversity loss, threatening up to 15-30% of described species by the end of the twenty-first century. We estimated the current suitable habitat and forecasted future distribution ranges of Indian pangolin (Manis crassicaudata) under climate change scenarios. We collected occurrence records of Indian pangolin using burrow counts, remote camera records and previously published literature in Pakistan during 2021-2023. We downloaded bioclimatic data for current (1970-2000) and future (2041-2060, 2061-2080, 2081-2100) climate scenarios from the WorldClim database using the Hadley Global Environment Model (HadGEM3-GC31-LL). We used MaxEnt software to predict current and future distributions of Indian pangolin, then computed the amount of habitat lost, gained, and unchanged across periods. We obtained 560 Indian pangolin occurrences overall, 175 during the study, and 385 from our literature search. Model accuracy was very good (AUC = 0.885, TSS = 0.695), and jackknife tests of variable importance showed that the contribution of annual mean temperature (bio1) was greatest (33.4%), followed by the mean temperature of the coldest quarter (bio-12, 29.3%), temperature seasonality (bio 4, 25.9%), and precipitation seasonality (bio 15, 11.5%). The maxent model predicted that during the current time period (1970-2000) highly suitable habitat for Indian pangolin was (7270 km2, 2.2%), followed by moderately suitable (12,418 km2, 3.7%), less suitable (49,846 km2, 14.8%), and unsuitable habitat (268,355 km2, 79.4%). Highly suitable habitat decreased in the western part of the study area under most SSPs and in the central parts it declined under all SSPs and in future time periods. The predicted loss in the suitable habitat of the Indian pangolin was greatest (26.97%) under SSP 585 followed by SSP 126 (23.67%) during the time 2061-2080. The gain in suitable habitat of Indian pangolin was less than that of losses on average which ranged between 1.91 and 13.11% under all SSPs during all time periods. While the stable habitat of the Indian pangolin ranged between 64.60 and 83.85% under all SSPs during all time periods. Our study provides the current and future habitat ranges of Indian pangolin in the face of a changing climate. The findings of our study could be helpful for policymakers to set up conservation strategies for Indian pangolin in Pakistan.

SAR, Molecular Docking and Molecular Dynamic Simulation of Natural Inhibitors against SARS-CoV-2 Mpro Spike Protein.

The SARS-CoV-2 virus and its mutations have affected human health globally and created significant danger for the health of people all around the world. To cure this virus, the human Angiotensin Converting Enzyme-2 (ACE2) receptor, the SARS-CoV-2 main protease (Mpro), and spike proteins were found to be likely candidates for the synthesis of novel therapeutic drug. In the past, proteins were capable of engaging in interaction with a wide variety of ligands, including both manmade and plant-derived small molecules. Pyrus communis L., Ginko bibola, Carica papaya, Syrian rue, and Pimenta dioica were some of the plant species that were studied for their tendency to interact with SARS-CoV-2 main protease (Mpro) in this research project (6LU7). This scenario investigates the geometry, electronic, and thermodynamic properties computationally. Assessing the intermolecular forces of phytochemicals with the targets of the SARS-CoV-2 Mpro spike protein (SP) resulted in the recognition of a compound, kaempferol, as the most potent binding ligand, -7.7 kcal mol-1. Kaempferol interacted with ASP-187, CYS-145, SER-144, LEU 141, MET-165, and GLU-166 residues. Through additional molecular dynamic simulations, the stability of ligand-protein interactions was assessed for 100 ns. GLU-166 remained intact with 33% contact strength with phenolic OH group. We noted a change in torsional conformation, and the molecular dynamics simulation showed a potential variation in the range from 3.36 to 7.44 against a 45-50-degree angle rotation. SAR, pharmacokinetics, and drug-likeness characteristic investigations showed that kaempferol may be the suitable candidate to serve as a model for designing and developing new anti-COVID-19 medicines.

Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes.

Calixarenes, as novel organic materials, can play a pivotal role in the development of high-performance nonlinear optical materials due to the ease of design and fabrication. In this study, DFT simulations were employed to investigate the geometric, electronic, and NLO responses of calix[4]arene doped with Li3O, Na3O, and K3O superalkalis. The computed values of the vertical ionization energies and interaction energies indicate the chemical and thermodynamic stabilities of the targeted M3O@calix[4]arene complexes. The corresponding energy gaps (2.01 to 3.49 eV) are notably reduced, indicating the semiconductor nature of the materials. Surprisingly, the M3O@calix[4]arene complexes exhibit transparency in the UV/visible range as the absorption peaks are shifted in the near infrared (NIR) region. The highest values of 5.9 × 105 a.u. and 2.3 × 108 a.u. for the respective first and second hyperpolarizabilities are observed for Na3O@calix[4]arene. Furthermore, the Na3O@calix[4]arene complex exhibits maximum values of 2.3 × 105 a.u. for second harmonic generation (SHG) and (K3O@calix[4]arene) 2.3 × 106 a.u. for the electro-optical Pockels effect (EOPE) at 1064 nm. Similarly, approximations are made for the dynamic second hyperpolarizability coefficients (EOKE and EFISHG) at different wavelengths. Notably, the Na3O@calix[4]arene complex demonstrates the highest quadratic nonlinear refractive index (n2) of 9.5 × 10-15 cm2 W-1 at 1064 nm. This research paves the way for the development of stable calix[4]arenes doped with superalkalis, leading to an improved nonlinear optical (NLO) response.

Predicting the Length of Stay of Cardiac Patients Based on Pre-Operative Variables-Bayesian Models vs. Machine Learning Models.

Length of stay (LoS) prediction is deemed important for a medical institution's operational and logistical efficiency. Sound estimates of a patient's stay increase clinical preparedness and reduce aberrations. Various statistical methods and techniques are used to quantify and predict the LoS of a patient based on pre-operative clinical features. This study evaluates and compares the results of Bayesian (simple Bayesian regression and hierarchical Bayesian regression) models and machine learning (ML) regression models against multiple evaluation metrics for the problem of LoS prediction of cardiac patients admitted to Tabba Heart Institute, Karachi, Pakistan (THI) between 2015 and 2020. In addition, the study also presents the use of hierarchical Bayesian regression to account for data variability and skewness without homogenizing the data (by removing outliers). LoS estimates from the hierarchical Bayesian regression model resulted in a root mean squared error (RMSE) and mean absolute error (MAE) of 1.49 and 1.16, respectively. Simple Bayesian regression (without hierarchy) achieved an RMSE and MAE of 3.36 and 2.05, respectively. The average RMSE and MAE of ML models remained at 3.36 and 1.98, respectively.

Exploring the Sensing Potential of g-C3N4 versus Li/g-C3N4 Nanoflakes toward Hazardous Organic Volatiles: A DFT Simulation Study.

Ab initio calculations were performed to determine the sensing behavior of g-C3N4 and Li metal-doped g-C3N4 (Li/g-C3N4) quantum dots toward toxic compounds acetamide (AA), benzamide (BA), and their thio-analogues, namely, thioacetamide (TAA) and thiobenzamide (TAA). For optimization and interaction energies, the ωB97XD/6-31G(d,p) level of theory was used. Interaction energies (Eint) illustrate the high thermodynamic stabilities of the designed complexes due to the presence of the noncovalent interactions. The presence of electrostatic forces in some complexes is also observed. The observed trend of Eint in g-C3N4 complexes was BA > TAA > AA > TBA, while in Li/g-C3N4, the trend was BA > AA > TBA > TAA. The electronic properties were studied by frontier molecular orbital (FMO) and natural bond orbital analyses. According to FMO, lithium metal doping greatly enhanced the conductivity of the complexes by generating new HOMOs near the Fermi level. A significant amount of charge transfer was also observed in complexes, reflecting the increase in charge conductivity. NCI and QTAIM analyses evidenced the presence of significant noncovalent dispersion and electrostatic forces in Li/g-C3N4 and respective complexes. Charge decomposition analysis gave an idea of the transfer of charge density between quantum dots and analytes. Finally, TD-DFT explained the optical behavior of the reported complexes. The findings of this study suggested that both bare g-C3N4 and Li/g-C3N4 can effectively be used as atmospheric sensors having excellent adsorbing properties toward toxic analytes.

Historical and current distribution ranges of the Asiatic black bear (Ursus thibetanus).

The current distribution of Asiatic black bear (Ursus thibetanus) is available on the IUCN Red List of Threatened species website; however, nothing is known about the historical extent and occurrence of this species. Therefore, we aimed to understand the historical distribution of the Asiatic black bear, and map and estimate its total size, to compare it with that of species current distribution. In addition, we analyzed a network of protected areas in the past and current ranges of the species. We employed geographic information system (GIS) software to reconstruct and measure the historical range of the Asiatic black bear, comparing past and current ranges to analyze its expected range contraction. The main focus of the study was to enhance our understanding of the species' historical distribution, contributing to better conservation strategies for the present and future perspectives. The utilization of GIS tools facilitates a comprehensive exploration of the factors influencing the species' decline, ultimately aiding in more effective management and conservation efforts. We used published records of black bear's occurrence in anywhere in history to reconstruct its historical distribution range. Results revealed that the Asiatic black bear was more widely distributed in historical times and its range spanned across approximately 15.86 million km2 while its current range is limited to approximately 7.85 million km2, showing a range contraction of approximately 49.5% (8.02 million km2 reduced). The total protected areas in the historical range of the species were found to be N = 9933, with total size of 0.946 million km2, against N = 6580 (0.667 million km2) that are present in the current range. Approximately 27.5% of the protected areas have lost the Asiatic black bear since historical times.

Frequency-dependent nonlinear optical response and refractive index investigation of lactone-derived thermochromic compounds.

Nonlinear optical (NLO) switchable materials play a crucial role in the fields of electronics and optoelectronics. The selection of an appropriate switching approach is vital in designing such materials to enhance their NLO response. Among various approaches, thermos-switching materials have shown a 4-fold increase in NLO response compared to other photo-switching materials. In this study, we computationally investigated the geometric, electronic, and nonlinear optical properties of reversible lactone-based thermochromic compounds using the ωB97XD/6-311+G (d,p) level of theory. Molecular orbital studies are employed to analyze the electronic properties of the close and open isomers of these compounds, while time-dependent density functional theory (TD-DFT) analysis is utilized to evaluate their molecular absorption. Our findings reveal that the π-electronic conjugation-induced delocalization significantly influences the ON-OFF switchable nonlinear optical response of the lactone-based thermochromic compounds. Notably, among all compounds, the open isomer of lactone 2 exhibits the highest hyperpolarizability value (6596.69 au). Furthermore, we extended our analysis to investigate the frequency-dependent second and third-order hyperpolarizabilities. The most pronounced frequency-dependent NLO response is observed at 532 nm. Additionally, we calculated the refractive index of these thermochromic compounds to further assess their nonlinear optical response. The open isomer of lactone 1 demonstrates the highest refractive index value (3.99 × 10-14 cm2/W). Overall, our study highlights the excellent potential of reversible thermochromic compounds as NLO molecular thermos-switches for future applications.

Repercussion of Primary Nucleation Pathway: Dementia and Cognitive Impairment.

Neurodegenerative diseases, such as Alzheimer's, Parkinson's, and prion disease, are characterized by the conversion of normally soluble proteins or peptides into aggregated amyloidal fibrils. These diseases result in the permanent loss of specific types of neurons, making them incurable and devastating. Research on animal models of memory problems mentioned in this article contributes to our knowledge of brain health and functionality. Neurodegenerative disorders, which often lead to cognitive impairment and dementia, are becoming more prevalent as global life expectancy increases. These diseases cause severe neurological impairment and neuronal death, making them highly debilitating. Exploring and understanding these complex diseases offer significant insights into the fundamental processes essential for maintaining brain health. Exploring the intricate mechanisms underlying neurodegenerative diseases not only holds promise for potential treatments but also enhances our understanding of fundamental brain health and functionality. By unraveling the complexities of these disorders, researchers can pave the way for advancements in diagnosis, treatment, and ultimately, improving the lives of individuals affected by neurodegenerative diseases.

Unveiling the Potential of B3O3 Nanoflake as Effective Transporter for the Antiviral Drug Favipiravir: Density Functional Theory Analysis.

In this study, for the first time, boron oxide nanoflake is analyzed as drug carrier for favipiravir using computational studies. The thermodynamic stability of the boron oxide and favipiravir justifies the strong interaction between both species. Four orientations are investigated for the interaction between the favipiravir and the B3O3 nanoflake. The Eint of the most stable orientation is -26.98 kcal/mol, whereas the counterpoise-corrected energy is -22.59 kcal/mol. Noncovalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses are performed to obtain insights about the behavior and the types of interactions that occur between B3O3 nanoflake and favipiravir. The results indicate the presence of hydrogen bonding between the hydrogen in the favipiravir and the oxygen in the B3O3 nanoflake in the most stable complex (FAV@B3O3-C1). The electronic properties are investigated through frontier molecular orbital analysis, dipole moments and chemical reactivity descriptors. These parameters showed the significant activity of B3O3 for favipiravir. NBO charge analysis transfer illustrated the charge transfer between the two species, and UV-VIS analysis confirmed the electronic excitation. Our work suggested a suitable drug carrier system for the antiviral drug favipiravir, which can be considered by the experimentalist for better drug delivery systems.

Study of Biochemical Parameters as Predictors for Need of Invasive Ventilation in Severely Ill COVID-19 Patients.

Background: Though laboratory tests have been shown to predict mortality in COVID-19, there is still a dearth of information regarding the role of biochemical parameters in predicting the type of ventilatory support that these patients may require. Methods: The purpose of our retrospective observational study was to investigate the relationship between biochemical parameters and the type of ventilatory support needed for the intensive care of severely ill COVID-19 patients. We comprehensively recorded history, physical examination, vital signs from point-of-care testing (POCT) devices, clinical diagnosis, details of the ventilatory support required in intensive care and the results of the biochemical analysis at the time of admission. Appropriate statistical methods were used and P-values < 0.05 were considered significant. Receiver operating characteristics (ROC) analysis was performed and Area Under the Curve (AUC) of 0.6 to 0.7, 0.7 to 0.8, 0.8 to 0.9, and >0.9, respectively, were regarded as acceptable, fair, good, and exceptional for discrimination. Results: Statistically significant differences (p<0.05) in Urea (p = 0.0351), Sodium (p = 0.0142), Indirect Bilirubin (p = 0.0251), Albumin (p = 0.0272), Aspartate Transaminase (AST) (p = 0.0060) and Procalcitonin (PCT) (p = 0.0420) were observed between the patients who were maintained on non-invasive ventilations as compared to those who required invasive ventilation. In patients who required invasive ventilation, the levels of Urea, Sodium, Indirect bilirubin, AST and PCT were higher while Albumin was lower. On ROC analysis, higher levels of Albumin was found to be acceptable indicator of maintenance on non-invasive ventilation while higher levels of Sodium and PCT were found to be fair predictor of requirement of invasive ventilation. Conclusion: Our study emphasizes the role of biochemical parameters in predicting the type of ventilatory support that is needed in order to properly manage severely ill COVID-19 patients.

Alkali metals doped cycloparaphenylene nanohoops: Promising nonlinear optical materials with enhanced performance.

In the ongoing pursuit of novel and efficient NLO materials, the potential of alkali metal-doped {6}cycloparaphenylene ({6}CPP) and methylene bridged {6} cycloparaphenylene (MB{6}CPP) nanohoops as excellent NLO candidates has been explored. The geometric, electronic, linear, and nonlinear optical properties of designed systems have been investigated theoretically. All the nanohoops demonstrated thermodynamic stability, with remarkable interaction energies reaching up to -1.39 eV (-0.0511 au). Notably, the introduction of alkali metals led to a significant reduction in the HOMO-LUMO energy gaps, with values as low as 2.92 eV, compared to 6.80 eV and 6.06 eV for undoped {6}CPP and MB{6}CPP, respectively. Moreover, the alkali metal-doped nanohoops exhibited exceptional NLO response, with the K@r6-{6}CPP complex achieving the highest first hyperpolarizability of 56,221.7 × 10-30 esu. Additionally, the frequency-dependent first hyperpolarizability values are also computed at two commonly used wavelengths of 1550 nm and 1907 nm, respectively. These findings highlight the potential of designed nanohoops as promising candidates for advanced NLO materials with high-tech applications.

Decorating Mg12O12 Nanocage with Late First-Row Transition Metals To Act as Single-Atom Catalysts for the Hydrogen Evolution Reaction.

In the pursuit of sustainable clean energy sources, the hydrogen evolution reaction (HER) has attained significant interest from the scientific community. Single-atom catalysts (SACs) are among the most promising candidates for future electrocatalysis because they possess high thermal stability, effective electrical conductivity, and excellent percentage atom utilization. In the present study, the applicability of late first-row transition metals (Fe-Zn) decorated on the magnesium oxide nanocage (TM@Mg12O12) as SACs for the HER has been studied, via density functional theory. The late first-row transition metals have been chosen as they have high abundance and are relatively low-cost. Among the studied systems, results show that the Fe@Mg12O12 SAC is the best candidate for catalyzing the HER reaction as it exhibits the lowest activation barrier for HER. Moreover, Fe@Mg12O12 shows high stability (Eint = -1.64 eV), which is essential in designing SACs to prevent aggregation of the metal. Furthermore, the results of the electronic properties' analysis showed that the HOMO-LUMO gap of the nanocage is decreased significantly upon doping of Fe (from 4.81 to 2.28 eV), indicating an increase in the conductivity of the system. This study highlights the potential application of the TM@nanocage SAC systems as effective HER catalysts.

Genomic analysis of wolves from Pakistan clarifies boundaries among three divergent wolf lineages.

Among the three main divergent lineages of gray wolf (Canis lupus), the Holarctic lineage is the most widespread and best-studied, particularly in North America and Europe. Less is known about Tibetan (also called Himalayan) and Indian wolf lineages in southern Asia, especially in areas surrounding Pakistan where all three lineages are thought to meet. Given the endangered status of the Indian wolf in neighboring India and unclear southwestern boundary of the Tibetan wolf range, we conducted mitochondrial and genome-wide sequencing of wolves from Pakistan and Kyrgyzstan. Sequences of the mitochondrial D-loop region of 81 wolves from Pakistan indicated contact zones between Holarctic and Indian lineages across the northern and western mountains of Pakistan. Reduced-representation genome sequencing of 8 wolves indicated an east-to-west cline of Indian to Holarctic ancestry, consistent with a contact zone between these two lineages in Pakistan. The western boundary of the Tibetan lineage corresponded to the Ladakh region of India's Himalayas with a narrow zone of admixture spanning this boundary from the Karakoram Mountains of northern Pakistan into Ladakh, India. Our results highlight the conservation significance of Pakistan's wolf populations, especially the remaining populations in Sindh and Southern Punjab that represent the highly endangered Indian lineage.

Robust and facile detection of formaldehyde through transition metals doped olympicene sensors: a step forward DFT investigation.

Formaldehyde, a volatile organic compound (VOC) released by building and decoration materials, has many applications in the chemical feedstock industry. Excessive release of formaldehyde can cause serious health issues, such as chest tightness, cough, cancer, and tissue damage. Therefore, detection of formaldehyde is required. Herein transition metal (Fe, Ni, and Pd) doped olympicene is evaluated as a gas sensor for the detection of formaldehyde. The performance of the designed electrochemical sensor is evaluated through interaction energy, natural bond orbital (NBO) non-covalent interaction (NCI), electron density differences (EDD), electrostatic potential (ESP), quantum theory of atom in molecule (QTAIM), frontier molecular orbital (FMO), and density of states (DOS) analysis. Interaction energies obtained at B3LYP-D3/def-2 TZVP level of theory shows that formaldehyde is physiosorbed over the surface of transition metal doped olympicene. The trend for interaction energy is OLY(Ni)/HCHO > OLY(Fe)/HCHO > OLY(Pd)/HCHO. The presence of non-covalent interactions is confirmed by the QTAIM and NCI analyses, while transfer of charges is confirmed by natural bond orbital analysis. The reduced density gradient (RDG) approach using noncovalent interaction (NCI) analysis demonstrates that electrostatic hydrogen bonding interactions prevail in the complexes. Recovery time is calculated to check the reusability of the sensor. This study may provide a deep insight for the designing of highly efficient electrochemical sensor against formaldehyde with transition metals doped on olympicene.

Enhanced nonlinear optical response of alkalides based on stacked Janus all-cis-1,2,3,4,5,6-hexafluorocyclohexane.

Significant efforts are continuously exerted by the scientific community to explore new strategies to design materials with high nonlinear optical responses. An effective approach is to design alkalides based on Janus molecules. Herein, we present a new approach to remarkably boost the NLO response of alkalides by stacking the Janus molecules. Alkalides based on stacked Janus molecule, M-n-M' (where n = 2 & 3 while M and M' are Li/Na/K) are studied for structural, energetic, electrical, and nonlinear optical properties. The thermodynamic stability of the designed complexes is confirmed by the energetic stabilities, which range between -14.07 and -28.77 kcal/mol. The alkalide character of alkali metals-doped complexes is confirmed by the NBO charge transfer and HOMO(s) densities. The HOMO densities are located on the doped alkali metal atoms, indicating their alkalide character. The absorptions in UV-Vis and near IR region confirm the deep ultraviolet transparency of the designed complexes. The maximum first static and dynamic hyperpolarizabilities of 5.13 × 107 and 6.6 × 106 au (at 1339 nm) confirm their high NLO response, especially for K-2-M' complexes. The NLO response of alkalides based on stacked Janus molecules is 1-2 orders of magnitude higher than the alkalide based on Janus monomer. The high values of dc-Kerr and electric field-induced response e.g., max ∼107 and 108 au, respectively have been obtained. These findings suggest that our designed complexes envision a new insight into the rational design of stable high NLO performance materials.

Role of Delocalization, Asymmetric Distribution of π-Electrons and Elongated Conjugation System for Enhancement of NLO Response of Open Form of Spiropyran-Based Thermochromes.

Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10-17 cm2/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics.

Complications and Outcomes of the Internal Fixation of Non-displaced Femoral Neck Fracture in Old Patients: A Two-Year Follow-Up.

Background Fractures of the proximal femur are amongst the most common injuries in the elderly population. While there is a clear consensus regarding the management of displaced femoral neck fractures, the management of non-displaced fractures is less clear. Both fixation and arthroplasty are valid treatment options. Internal fixation is a less invasive procedure, but it carries the risks of non-union and avascular necrosis (AVN) of the femoral head. The literature describes varying complication rates associated with these risks. We aim to describe a series of elderly patients above the age of 65 years with non-displaced fractures of the femoral neck who were treated with internal fixation. Our objectives are to determine the union rate and complications in this group and to elucidate the factors that influence these outcomes. Methods We conducted a retrospective review of all patients aged 65 years and older who presented with femoral neck fractures at our level 1 trauma unit between 2018 and 2020. Fractures were classified using the Garden classification system, and only those with Garden 1 or 2 fractures (non-displaced) were included. Preoperative radiographs or intraoperative fluoroscopy images were used to classify fractures using the Pauwels classification. Serial postoperative radiographs and clinical notes (up to 24 months postoperatively) were reviewed to assess the union rate and the development of complications. Both non-union and AVN were analysed for their associations with age, sex, Pauwels grade and comorbidities. A subgroup analysis of the complications was performed to elucidate their association with age groups (<80 and >80 years) and types of fixations (dynamic hip screws {DHS} and cannulated screws). Results A total of 148 patients, consisting of 60 males and 88 females, were included in the analysis. The patients had a mean age of 78.5 years (ranging from 65 to 98 years). The union rate without any degree of AVN was 90.7%, with six non-unions (4.05%) and six patients experiencing AVN (4.05%). No difference in outcome was detected between the two groups based on age. High (type 2 or 3) Pauwels grade (p = 0.05) and treatment with cannulated screws (p = 0.02) were indicated as significant factors for non-union. All patients who developed AVN were noted to have a comorbidity that is known to predispose them to AVN. Conclusion Our series shows a union rate of 90.7%, which is comparable to the union rates reported in other published literature. Our results suggest that age does not independently influence the outcome of fixation for these fractures. We conclude that fractures with vertical orientation (Pauwels grade 2 or 3), when treated with cannulated screws, are more likely to result in non-union. AVN is the second most common complication after non-union, which is also associated with other risk factors for AVN.

Giant NLO response and deep ultraviolet transparency of dual (alkali/alkaline earth) metals doped C6O6Li6 electrides.

The designing of new materials having outstanding nonlinear optical (NLO) response is much needed for use in latest optics. Herein, the geometric, electronic and NLO properties of alkali and alkaline earth metals doped C6O6Li6 (alk-C6O6Li6-alkearth, alkearth = Ca, Mg, Be and alk = K, Na, Li) electrides is studied via quantum chemical approach. The interaction energies (Eint) are examined to illustrate their thermodynamic stability. The strong interaction energy of -39.99 kcal mol-1 is observed for Ca-C6O6Li6-Li electride in comparison to others. Frontier molecular orbitals (FMOs) energy gap of considered complexes is changed due to the electronic density shifting between metals and C6O6Li6 surface, which notifies the semi conducting properties of these electrides. The FMOs isodensities and natural bond orbital (NBO) charge analysis are performed to justify charge transfer between dopants and complexant. UV-Visible study also confirmed the application of these electrides as deep ultra-violet laser devices. NLO response is studied through calculation of first hyperpolarizability (ßo). The highest ßo value of 1.68 × 105 au is calculated for Mg-C6O6Li6-K electride. NLO response is further rationalized by three- and two-level models approach.