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A Spanish-speaking farm worker with type 2 diabetes mellitus presented to our institution with an ulcerating tongue lesion. He was initially evaluated for possible squamous cell carcinoma; however, histologic examination revealed coccidioidomycosis. Coccidioidal titers were elevated and consistent with disseminated disease, although the patient had no systemic symptoms and clinical evaluation was negative. He was ultimately treated with intravenous and oral antifungal medication, which was followed by improvement of his tongue lesion. [ABSTRACT FROM AUTHOR]

Biochar has emerged as a promising soil amendment material, offering the potential to enhance mechanical and water retention properties. Geo-environmental structures constructed with biochar-amended soils (BAS) might experience a change in strength and water retention capacity due to extreme climactic changes, resulting in structural failures. The existing literature lacks a comprehensive study on the strength of BAS under prolonged curing, freeze-thaw cycles, and water retention behaviour for varying compaction conditions. The current study focused on addressing this research gap. Bamboo biochar (BB) was mixed with lean clay (CL) and silty sand (SM) in five different percentages (0%, 1%, 2%, 3.5% and 5% w/w) to prepare BAS specimens for unconfined compressive strength (UCS) and water retention tests. Results showed that UCS of CL soil increased up to 2% BB content but decreased thereafter, whereas it consistently decreased for SM soil with increasing BB content. Irrespective of the BB content, both soils consistently showed an increase in UCS with the curing period, which can be attributed to the enhanced bonding between the soil and BB, as well as the formation of stable aggregates. In contrast, the strength of both biochar-amended soils (BAS) decreased with the increase in freeze-thaw cycles, due to the expansion and contraction of ice within the specimen. The porous and hydrophilic nature of biochar (BB) increased the water retention capacity of both soils, with a more significant improvement observed in CL soil compared to SM soil, under both compacted and slurry conditions. Specimen compaction significantly decreased the gravimetric water content at the permanent wilting point in both soils. These variations were also evident in the microstructural analysis., Competing Interests: Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

This report presents a silver-mediated site-selective chalcogenation of tryptophan-containing peptides with various dichalcogenides (disulfides/diselenides) at room temperature in good to excellent yields. The significant features include broad substrate scope, functional group diversity, late-stage modification of drug molecules (Dopamine and Levodopa), and various valuable postsynthetic transformations under mild conditions.

This report describes a Pd-catalyzed picolinamide-directed site-selective C(sp 2 )-H sulfonylation of amino acids and peptides with sodium sulfinates in moderate to good yields. Sulfonylation of levodopa and dopamine drug molecules and late-stage directed peptide sulfonylation are studied for the first time. Broad substrate scope having various functionalities, late-stage drug modifications, and various post synthetic utilities such as chalcogenation, bromination, olefination, and arylation are potential advantages.

Chromoblastomycosis (CBM), also known as chromomycosis is a chronic, granulomatous fungal infection of the skin and subcutaneous tissue. It usually occurs by the traumatic inoculation of various dematiaceous fungi and is more common in the developing world. This condition is rare in North America and the developed world. Herein, we present a case of a 75-year-old man who received a bilateral lung transplant 4 months prior and presented for evaluation of a painful, erythematous papule on the elbow which was diagnosed as CBM. This case highlights that immunosuppression used in patients who undergo solid organ transplantation not only increases the risk of opportunistic infections like CBM but can also be confused for cutaneous squamous cell carcinoma as both these entities share many overlapping clinical and histopathologic features and may be a potential source of misdiagnosis., Competing Interests: Declaration of competing interest This is a conflict-of-interest statement accompanying a manuscript by Leela Krishna Teja Boppana, MD, et al titled “Chromoblastomycosis: A potential Mimic of Squamous Cell Carcinoma in Transplant Recipients.” I hereby declare that none of the authors has potential conflict of interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The realization and discovery of quantum spin liquid (QSL) candidate materials are crucial for exploring exotic quantum phenomena and applications associated with QSLs. Most existing metal-organic two-dimensional (2D) quantum spin liquid candidates have structures with spins arranged on the triangular or kagome lattices, whereas honeycomb-structured metal-organic compounds with QSL characteristics are rare. Here, we report the use of 2,5-dihydroxy-1,4-benzoquinone (X 2 dhbq, X = Cl, Br, H) as the linkers to construct cobalt(II) honeycomb lattices (NEt 4 ) 2 [Co 2 (X 2 dhbq) 3 ] as promising Kitaev-type QSL candidate materials. The high-spin d 7 Co 2+ has pseudospin-1/2 ground-state doublets, and benzoquinone-based linkers not only provide two separate superexchange pathways that create bond-dependent frustrated interactions but also allow for chemical tunability to mediate magnetic coupling. Our magnetization data show antiferromagnetic interactions between neighboring metal centers with Weiss constants from -5.1 to -8.5 K depending on the X functional group in X 2 dhbq linkers (X = Cl, Br, H). No magnetic transition or spin freezing could be observed down to 2 K. Low-temperature susceptibility (down to 0.3 K) and specific heat (down to 0.055 K) of (NEt 4 ) 2 [Co 2 (H 2 dhbq) 3 ] were further analyzed. Heat capacity measurements confirmed no long-range order down to 0.055 K, evidenced by the broad peak instead of the λ-like anomaly. Our results indicate that these 2D cobalt benzoquinone frameworks are promising Kitaev QSL candidates with chemical tunability through ligands that can vary the magnetic coupling and frustration.

Electrochemical dearomatization has been recognized as an attractive tool for the rapid construction of structurally diverse molecules. The designed methodology encompasses an eco-friendly and efficient electrochemical approach to synthesizing spiro[4.5]dienones under mild reaction conditions. Furthermore, detailed mechanistic studies strongly bolster our hypothesis and emphasize the role of HFIP in the mechanism. The protocol is scalable and showcases a broad substrate scope with tolerance toward numerous functional groups. Henceforth, this strategy can be deployed as an alternative and sustainable tool for accessing spiro[4.5]dienones.

This manuscript describes the syntheses, structures and magnetism of Mn III -Ca II /Sr II complexes which are compositionally relevant in the context of the oxygen evolving complex (OEC) of photosystem II (PS II). A series of trimetallic tetraoxo complexes containing redox-inactive metal ions Ca II or Sr II were synthesized using a tetranucleating ligand framework. The structural characteristics of these complexes, with the oxido ligands bridging the redox-inactive metals and the manganese centres, make them particularly relevant to biological and heterogeneous metal-oxido clusters. Electrochemical studies of these compounds show that the reduction potentials are highly dependent upon the Lewis acidity of the redox-inactive metal, identifying the chemical basis for the observed differences in electrochemistry. This correlation provides insights into the role of the Ca II /Sr II ion in modulating the redox potential of the OEC and of other redox-inactive ions in tuning the redox potentials of other metal-oxide electrocatalysts. Temperature dependent magnetic measurements have also been performed for the complexes.

This report describes the Pd-catalyzed late-stage chalcogenation of tryptophan-containing peptides with disulfides/diselenides in moderate to good yields. It comprises broad substrate scope, functional group diversity, late-stage modification of drug molecules, and various valuable synthetic transformations, including room temperature easy removal of the picolinamide auxiliary, which could be applicable to tune the structure and function of peptides.

Herein, we have utilized 2-(2-hydroxyphenyl)benzimidazole (HBI) to synthesize 3-(1H-benzoimidazol-2-yl)-2-hydroxy-5-methyl-benzaldehyde (HBIA) followed by three Schiff bases by using -ortho (H 2 BIo), -meta (H 3 BIdm) and -para (H 2 BIp) substituted amino benzoic acids and studied their photophysical properties. We have successfully derived molecular structures of HBI, HBIA and H 3 BIdm which reveals that in HBI and HBIA, the phenolic -OH is intramolecularly hydrogen bonded with sp 2 N of benzimidazole group whereas in H 3 BIdm, it is hydrogen bonded with imine C=N of Schiff base moiety, which is responsible for different solid state emission properties of the reported compounds. Extensive experimental and theoretical studies show that for all three Schiff bases, in solution due to activation of C=N isomerization, ESIPT operates through benzimidazole site and displays different emission from the solid state. Furthermore, H 2 BIo, H 3 BIdm and H 2 BIp selectively sense Cu 2+ in semi aqueous medium with nano-molar detection limit and in HuH-7 cells through the inhibition of ESIPT of process., (© 2023 Wiley-VCH GmbH.)

Biochar is a carbon-rich stable product derived from the thermochemical decomposition of biomass. The properties of biochar vary with types of feedstock, heating rate, pyrolysis temperature, etc. Consequently, the mechanical and hydrological properties of biochar amended soil (BAS) also differ with types of biochar and soils. However, the effect of bamboo biochar (BB) amendment on soil strength and water retention properties is missing in the previous literature. Bamboo biomass was pyrolysed at 600 °C to produce biochar. BB and soils (low plastic clay (CL) and silty sand (SM)) were mixed to prepare BAS. The samples were prepared by mixing BB in five ratios, i.e., 0%, 1%, 2%, 3.5% and 5% of dry soil weight. The biochar application has increased optimum moisture content, alkalinity (pH) and Atterberg limits, whereas, reduced maximum dry density and specific gravity of both the soils (CL and SM). The unconfined compressive strength (UCS) of CL soil was noted to increase by 10.5% with 2% biochar content and decreased after that, whereas the UCS of SM soil was found to decrease continuously with the biochar content increment. Therefore, the unconfined compressive strength (UCS) result showed that biochar application has contrary effects on both soils. The measured gravimetric water content (GWC) of BAS was increased with biochar increment in both soils. However, GWC increased more in CL than in SM soil at the same biochar content. The microstructural analysis showed that the biochar amendment filled the pore space of the soil matrix, resulting in an increase in UCS and GWC values. The increased water retention capacity and strength (UCS) of biochar amended CL soil provides evidence that it could be used as a landfill cover material., (© 2023. The Author(s).)

Pulmonary fibrosis (PF) is characterized by profound scarring and poor survival. We investigated the association of leukocyte telomere length (LTL) with chronological age and mortality across racially diverse PF cohorts. LTL measurements among participants with PF stratified by race/ethnicity were assessed in relation to age and all-cause mortality, and compared to controls. Generalized linear models were used to evaluate the age-LTL relationship, Cox proportional hazards models were used for hazard ratio estimation, and the Cochran-Armitage test was used to assess quartiles of LTL. Standardized LTL shortened with increasing chronological age; this association in controls was strengthened in PF (R = -0.28; P < 0.0001). In PF, age- and sex-adjusted LTL below the median consistently predicted worse mortality across all racial groups (White, HR = 2.21, 95% CI = 1.79-2.72; Black, HR = 2.22, 95% CI = 1.05-4.66; Hispanic, HR = 3.40, 95% CI = 1.88-6.14; and Asian, HR = 2.11, 95% CI = 0.55-8.23). LTL associates uniformly with chronological age and is a biomarker predictive of mortality in PF across racial groups., (© 2023. The Author(s).)

Background: Guidelines on the management of acute pulmonary embolism (PE) recommend consideration of endovascular therapies (EVT) for patients at intermediate-high risk. However, long-term data on the outcomes of patients after EVT as compared to medical therapy is lacking. This study aimed to compare outcomes of patients receiving EVT as compared to medical therapy alone at 3 to 6 months., Methods: In this single-center, retrospective cohort study, 190 patients with PE underwent evaluation for presence of right ventricular (RV) dysfunction by transthoracic echocardiogram, residual perfusion defects on ventilation-perfusion scanning, and functional capacity by 6-minute walk distance (6MWD) at 3 to 6 month follow-up., Results: Fifty-eight (31%) patients received EVT for the management of their acute PE. At follow-up (median 120 [97-170] days), 71% of patients who received EVT had normalization of RV function compared with only 34% of patients who received medical therapy alone ( P < . 001). Patients who received EVT had a significantly greater increase in their estimated glomerular filtration rate ( P = . 001), decrease in N-terminal proB-type natriuretic peptide ( P = . 003), and decrease in hemoglobin values ( P = . 018). Patients with intermediate-high to high risk PE who received EVT had significantly greater distance achieved on their 6MWD as compared to those who received medical therapy alone ( P = . 025)., Conclusions: Patients with acute PE who received EVT plus medical therapy were more likely to achieve normalization of RV dysfunction at 3 to 6 month follow-up compared to patients who received medical therapy alone. These data suggest that EVT is an effective therapy option for acute PE in intermediate-high and high risk patients with potential durable long-term benefits., (© 2023 The Authors.)

Studying multi-particle elementary excitations has provided unique access to understand collective many-body phenomena in correlated electronic materials, paving the way towards constructing microscopic models. In this work, we perform O K -edge resonant inelastic X-ray scattering (RIXS) on the quasi-one-dimensional cuprate Sr 14 Cu 24 O 41 with weakly-doped spin ladders. The RIXS signal is dominated by a dispersing sharp mode ~ 270 meV on top of a damped incoherent component ~ 400-500 meV. Comparing with model calculations using the perturbative continuous unitary transformations method, the two components resemble the spin-conserving ΔS = 0 two-triplon bound state and continuum excitations in the spin ladders. Such multi-spin response with long-lived ΔS = 0 excitons is central to several exotic magnetic properties featuring Majorana fermions, yet remains unexplored given the generally weak cross-section with other experimental techniques. By investigating a simple spin-ladder model system, our study provides valuable insight into low-dimensional quantum magnetism., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2023.)

The pyrochlore iridates (Eu1-xBi x ) 2 Ir 2 O 7 (0⩽ x ⩽1) undergo an anomalous negative lattice expansion for small Bi-doping (x⩽0.035) (region I) and a normal lattice expansion forx⩾0.1(region II); this is accompanied by a transition from an insulating (and magnetically ordered) to a metallic (and with no magnetic ordering) ground state. Here, we investigate (Eu1-xBi x ) 2 Ir 2 O 7 (0⩽ x ⩽1) using hard x-ray photoemission spectroscopy and x-ray absorption fine structure (XAFS) spectroscopy. By analyzing the Eu- L 3 , Ir- L 3 and Bi- L 2 & L 3 edges x-ray absorption near edge structure spectra and Eu-3 d core-level XPS spectra, we show that the metal cations retain their nominal valence, namely, Ir 4+ , Bi 3+ and Eu 3+ , respectively, throughout the series. The Ir-4 f and Bi-4 f core-level XPS spectra consist of screened and unscreened doublets. The unscreened component is dominant In the insulating range (x⩽0.035), and in the metallic region (x⩾0.1), the screened component dominates the spectra. The Eu-3 d core-level spectra remain invariant under Bi doping. The extended XAFS data show that the coordination around the Ir remains well preserved throughout the series. The evolution of the valence band spectra near the Fermi energy with increasing Bi doping indicates the presence of strong Ir(5d)-Bi(6p) hybridization which drives the metal-to-insulator transition., (© 2022 IOP Publishing Ltd.)

Chronic thromboembolic pulmonary hypertension (CTEPH), defined as precapillary pulmonary hypertension (PH) by right heart catheterization and imaging consistent with chronic thromboembolism, is a long-term complication of pulmonary embolism (PE). Pathobiological mechanisms involve pulmonary artery occlusion from organized thromboembolic material despite at least three months of uninterrupted therapeutic anticoagulation following acute PE and secondary microvasculopathy. Delay in diagnosis and management of CTEPH is associated with poor outcomes. High clinical suspicion, comprehensive assessment of residual dyspnea or exercise intolerance in the aftermath of PE and accurate interpretation of computed tomography pulmonary angiography (CTPA) are pivotal steps in the diagnosis. Ventilation-perfusion (V/Q) scan is the preferred initial radiologic screening tool as normal V/Q essentially rules out CTEPH. Any mismatched perfusion defect on the V/Q scan in the setting of PH or any finding compatible with chronic thromboembolism on CTPA should prompt referral to an expert CTEPH center. Once the diagnosis is verified, all eligible patients should be offered pulmonary thromboendarterectomy (PTE). Pulmonary vasodilators or balloon pulmonary angioplasty are safe and effective in inoperable or post-PTE persistent/recurrent CTEPH. During the course of their disease, a patient may receive a combination of treatments, at times consisting of all three strategies. Lifelong therapeutic anticoagulation is recommended for CTEPH., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

This work facilitates detection of bivalent copper ion by a simple Schiff base probe QNH based on a quinoxaline-naphthaldehyde framework. The detailed study in absorption spectroscopy and theoretical aspects and crystal study of the probe and probe-copper complex has been discussed. The detection limit of the probe in the presence of Cu 2+ is 0.45 µM in HEPES-buffer/acetonitrile (3/7, v / v ) medium for absorption study. The reversibility of the probe-copper complex has been investigated by EDTA. The selective visual detection of copper has been established also in gel form.

Optical chemosensors caused a revolution in the field of sensing due to their high specificity, sensitivity, and fast detection features. Imidazole derivatives have offered promising features in the literature as they bear suitable donor/acceptor groups for the selective analytes in the skeleton. In this work, an isoindole-imidazole containing a Schiff base chemosensor (1-{3-[(2-Diethylamino-ethylimino)-methyl]-2-hydroxy-5-methyl-phenyl}-2H-imidazo[5,1-a]isoindole-3,5-dione) was designed and synthesized. The complete sensing phenomena have been investigated by means of UV-Vis, fluorescence, lifetime measurement, FT-IR, NMR and ESI-MS spectroscopic techniques. The optical properties of the synthesized ligand were investigated in 3:7 HEPES buffer:DMSO medium and found to be highly selective and sensitive toward Zn 2+ ion through a fluorescence turn-on response with detection limit of 0.073 μm. Furthermore, this response is effective in gel form also. The competition studies reveal that the response of the probe for Zn 2+ ion is unaffected by other relevant metal ions. The stoichiometric binding study was performed utilizing Job's method which indicated a 1:1 sensor-Zn 2+ ensemble. Computational calculations were performed to pinpoint the mechanism of sensing.

Pulmonary capillary hemangiomatosis (PCH) is an uncommon type of pulmonary vascular disease characterized by capillary proliferation and very poor prognosis owing to misdiagnosis and lack of effective therapeutic options. Mutations in the eukaryotic translation initiation factor 2α kinase 4 (EIF2AK4) gene have been reported in pulmonary veno-occlusive disease and PCH. In this report, we present a patient whose diagnosis of PCH was delayed by 2 ½ years despite prior surgical lung biopsy and clinical and laboratory findings suggestive of pulmonary hypertension. Genotyping revealed a novel likely pathogenic variant in the EIF2AK4 gene. Review of surgical lung biopsy performed 2 ½ years prior confirmed PCH histology along with constrictive bronchiolitis., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

We herein report two salicyaldehyde-quinoxaline (HQS and HQSN) conjugates and a benzaldehyde-quinoxaline (QBN) conjugate to fabricate selective chemosensors for F - and Hg 2+ in the micromolar range. This work demonstrates how sensing outcomes are affected by modulating proton acidity by introducing an electron donating group, -NEt 2 , in the probe backbone. Interestingly, the un-substituted probe HQS can selectively detect F - , whereas HQSN and QBN are selective for Hg 2+ . In order to gain insights into the mechanism of sensing, geometry optimizations have been carried out on QS (-1) , QS (-1) ⋅⋅⋅HF, QSN (-1) and QSN (-1) ⋅⋅⋅HF and the experimental data are validated in terms of free energy and pK a values. Detailed DFT and TD-DFT analyses provide ample support towards the mechanism of sensing of the analytes., (© 2021 Wiley-VCH GmbH.)

A triple-decker complex of tungsten, [(Cp*W) 2 {μ-η 6 :η 6 -B 4 H 4 Co 2 (CO) 5 }(H) 2 ] ( 1 ; Cp* = η 5 -C 5 Me 5 ), with a planar middle deck has been isolated by thermolysis of an in situ formed intermediate from the reaction of Cp*WCl 4 and LiBH 4 with Co 2 (CO) 8 . In addition, we have also isolated another triple-decker complex, [(Cp*W) 2 {μ-η 6 :η 6 -B 5 H 5 Fe(CO) 3 }(H) 2 ] ( 4 ), having a puckered central ring, from a similar reaction with Fe 2 (CO) 9 . Clusters 1 and 4 are unprecedented examples of a triple-decker complex having a 24-valence electron with bridging hydrogen atoms.

Hepatitis B virus (HBV) can be transmitted from organ donor to recipient, but details of transmission events are not widely published. The Disease Transmission Advisory Committee (DTAC) evaluated 105 cases of potential donor derived transmission events of HBV between 2009-2017. Proven, probable or possible transmission of HBV occurred in 25 (23.8%) cases. Recipients of liver grafts were most commonly infected (20 of 21 exposed recipients) compared to 9 of 21 exposed non-hepatic recipients. Eleven of 25 donors were HBV core antibody (HBcAb) positive/HBV surface antigen (HBsAg) negative and infected 8/20 recipients. Of the 10 liver recipients and 1 liver-kidney recipient who received organs from these donors: six were not given antiviral prophylaxis, two developed infection after antiviral prophylaxis was discontinued, two developed HBV while on lamivudine prophylaxis, one was on antiviral prophylaxis and did not develop HBV viremia or antigenemia. One recipient of a HBcAb positive/HBsAg negative kidney developed active HBV infection. Unexpected donor-derived transmission of HBV was a rare event in reports to DTAC, but was often detected in the recipient late post-transplant. Six of 11 recipients (54.5%) of a liver from a HBcAb positive donor did not receive prophylaxis; all of these were potentially preventable with the use of anti-viral prophylaxis., (© 2020 Wiley Periodicals LLC.)

Due to the outbreak of Coronavirus, humans all over the world are facing several health problems. The present study has explored the spatio-temporal pattern of Coronavirus spread in India including spatial clustering, identification of hotspot, spatial heterogeneity, and homogeneity, spatial trend, and direction of COVID-19 cases using spatial statistical analysis during the period of 30 January to 20 June 2020. Besides, the polynomial regression model has been used for predictions of COVID-19 affected population and related deaths. The study found positive spatial heterogeneity in COVID-19 cases in India. The study has also identified 17 epicentres across the country with high incidence rates. The directional distribution of ellipse polygon shows that the spread of COVID-19 now trending towards the east but the concentration of cases is mainly in the western part of the country. The country's trend of COVID-19 follows a fourth-order polynomial growth and is characterized by an increasing trend. The prediction results show that as on 14 October India will reach 14,660,400 COVID-19 cases and the death toll will cross 152,945. Therefore, a "space-specific" policy strategy would be a more suitable strategy for reducing the spatial spread of the virus in India. Moreover, the study has broadly found out seven sectors, where the Government of India lacks in terms of confronting the ongoing pandemic. The study has also recommended some appropriate policies which would be immensely useful for the administration to initiate strategic planning., (© 2020 The Author(s). Regional Science Policy and Practice © 2020 RSAI.)

COVID-19 originally known as Corona VIrus Disease of 2019, has been declared as a pandemic by World Health Organization (WHO) on 11th March 2020. Unprecedented pressures have mounted on each country to make compelling requisites for controlling the population by assessing the cases and properly utilizing available resources. The rapid number of exponential cases globally has become the apprehension of panic, fear and anxiety among people. The mental and physical health of the global population is found to be directly proportional to this pandemic disease. The current situation has reported more than twenty four million people being tested positive worldwide as of 27th August, 2020. Therefore, it is the need of the hour to implement different measures to safeguard the countries by demystifying the pertinent facts and information. This paper aims to bring out the fact that tweets containing all handles related to COVID-19 and WHO have been unsuccessful in guiding people around this pandemic outbreak appositely. This study analyzes two types of tweets gathered during the pandemic times. In one case, around twenty three thousand most re-tweeted tweets within the time span from 1st Jan 2019 to 23rd March 2020 have been analyzed and observation says that the maximum number of the tweets portrays neutral or negative sentiments. On the other hand, a dataset containing 226,668 tweets collected within the time span between December 2019 and May 2020 have been analyzed which contrastingly show that there were a maximum number of positive and neutral tweets tweeted by netizens. The research demonstrates that though people have tweeted mostly positive regarding COVID-19, yet netizens were busy engrossed in re-tweeting the negative tweets and that no useful words could be found in WordCloud or computations using word frequency in tweets. The claims have been validated through a proposed model using deep learning classifiers with admissible accuracy up to 81%. Apart from these the authors have proposed the implementation of a Gaussian membership function based fuzzy rule base to correctly identify sentiments from tweets. The accuracy for the said model yields up to a permissible rate of 79%., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2020 Elsevier B.V. All rights reserved.)

In an effort to generate triple-decker complexes comprising a {PdCl 2 }moiety in the middle deck, we have explored the reactivity of [(Cp*M) 2 {μ-B 2 H 2 E 2 }], 1 - 4 ( 1 : M = Co, E = S; 2 : M = Co, E = Se; 3 : M = Rh, E = Se; and 4 : M = Ir, E = Se; Cp* = η 5 -C 5 Me 5 ), with [PdCl 2 (COD)] (COD = 1,5-cyclooctadiene). The reactions led to the formation of a series of trinuclear heterometallic triple-decker complexes, [(Cp*M) 2 {μ-B 2 H 2 E 2 Pd(Cl) 2 }], 5 - 8 ( 5 : M = Co, E = S; 6 : M = Co, E = Se; 7 : M = Rh, E = Se; and 8 : M = Ir, E = Se). Formation of the complexes 5 - 8 occurred almost instinctively as a single product with the elimination of the COD ligand. These complexes are examples of novel triple-decker species having a planar bridging palladacycle ligand, in which the Pd metal exists as Pd(II) in an uncommon pseudo-octahedral environment with an elongated M-Pd bonding interaction. The new species, 5 - 8 , have been characterized spectroscopically, and the structures of 5 - 7 were confirmed by single-crystal X-ray diffraction studies. The structure and bonding of these molecules were further analyzed with the help of density functional theory studies that found a strong electron donation from the B 2 E 2 (E = S or Se) fragment of the middle ring to the axial metals, while a weak bonding interaction between group 9 metals and Pd.

Melanoma or malignant melanoma is a type of skin cancer that develops when melanocyte cells, damaged by excessive exposure to harmful UV radiations, start to grow out of control. Though less common than some other kinds of skin cancers, it is more dangerous because it rapidly metastasizes if not diagnosed and treated at an early stage. The distinction between benign and melanocytic lesions could at times be perplexing, but the manifestations of the disease could fairly be distinguished by a skilled study of its histopathological and clinical features. In recent years, deep convolutional neural networks (DCNNs) have succeeded in achieving more encouraging results yet faster and computationally effective systems for detection of the fatal disease are the need of the hour. This paper presents a deep learning-based 'You Only Look Once (YOLO)' algorithm, which is based on the application of DCNNs to detect melanoma from dermoscopic and digital images and offer faster and more precise output as compared to conventional CNNs. In terms with the location of the identified object in the cell, this network predicts the bounding box of the detected object and the class confidence score. The highlight of the paper, however, lies in its infusion of certain resourceful concepts like two phase segmentation done by a combination of the graph theory using minimal spanning tree concept and L-type fuzzy number based approximations and mathematical extraction of the actual affected area of the lesion region during feature extraction process. Experimented on a total of 20250 images from three publicly accessible datasets-PH2, International Symposium on Biomedical Imaging (ISBI) 2017 and The International Skin Imaging Collaboration (ISIC) 2019, encouraging results have been obtained. It achieved a Jac score of 79.84% on ISIC 2019 dataset and 86.99% and 88.64% on ISBI 2017 and PH2 datasets, respectively. Upon comparison of the pre-defined parameters with recent works in this area yielded comparatively superior output in most cases.

We provide spectroscopic evidence for the charge density wave (CDW) phason mode at ≈0.93 THz in the two-leg, spin-1/2 ladders of Sr 14 Cu 24 O 41 using terahertz time-domain spectroscopy. We find that annealing in an oxygen atmosphere or doping with a low concentration of Co (≾1%) does not affect the CDW phason mode. However, Co doping at higher concentrations (10%), wherein the Co enters the ladder layers, destabilizes the CDW. We believe that the suppression of the CDW phase is due to an increase in intraladder overlap integrals through the shrinkage of interplane distance upon Co doping.

Triply-bridging bis-{hydrido(borylene)} and bis-borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe 2 (CO) 9 ] with an in situ produced intermediate, generated from the low-temperature reaction of [Cp*WCl 4 ] (Cp*=η 5 -C 5 Me 5 ) and [LiBH 4 ⋅THF] afforded triply-bridging bis-{hydrido(borylene)}, [(μ 3 -BH) 2 H 2 {Cp*W(CO) 2 } 2 {Fe(CO) 2 }] (1) and bis-borylene, [(μ 3 -BH) 2 {Cp*W(CO) 2 } 2 {Fe(CO) 3 }] (2). The chemical bonding analyses of 1 show that the B-H interactions in bis-{hydrido (borylene)} species is stronger as compared to the M-H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO-LUMO for 2 as compared to 1. In an attempt to synthesize the ruthenium analogue of 1, a similar reaction has been performed with [Ru 3 (CO) 12 ]. Although we failed to get the bis-{hydrido(borylene)} species, the reaction afforded triply-bridging bis-borylene species [(μ 3 -BH) 2 {WCp*(CO) 2 } 2 {Ru(CO) 3 }] (2'), an analogue of 2. In search for the isolation of bridging bis-borylene species of Rh, we have treated [Co 2 (CO) 8 ] with nido-[(RhCp*) 2 (B 3 H 7 )], which afforded triply-bridging bis-borylene species [(μ 3 -BH) 2 (RhCp*) 2 Co 2 (CO) 4 (μ-CO)] (3). All the compounds have been characterized by means of single-crystal X-ray diffraction study; 1 H, 11 B, 13 C NMR spectroscopy; IR spectroscopy and mass spectrometry., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: The intravenous or subcutaneous delivery of prostanoid drugs for moderate to severe pulmonary arterial hypertension has been fraught with complications and patient dissatisfaction. Combination therapy including inhaled treprostinil is an attractive alternative in clinically stable patients. Uncertainties exist about the patient characteristics and the optimal setting (inpatient versus office/home) for transition., Methods: Sixteen stable patients with pulmonary arterial hypertension and favorable risk profile were transitioned from parenteral prostanoid to combination therapy including inhaled treprostinil in the home setting. Nine patients were using intravenous treprostinil, two patients were using subcutaneous treprostinil, and five patients were using intravenous epoprostenol at a median dose of 80 (interquartile range, IQR 72-90), 76.5 (68 and 85), and 28 (IQR 26-30) ng/kg/min respectively. Patients were followed up for a median of 732.5 days after transition (IQR 506.5-1294 days)., Results: Patients tolerated the transition to inhaled treprostinil well without significant change in functional class (81.25% FC I/II before transition vs. 87.5% after), 6-min walk distance [349 m (IQR 226-461 m) to 364 m (IQR 238-565 m), p = 0.09] or NT-proBNP [149 pg/ml (IQR 71.5-383 pg/ml) to 186.5 pg/ml (IQR 83.5-444 pg/ml), p = 0.38]. Hemodynamic data, where available, showed significant improvements in mean pulmonary artery pressure and pulmonary vascular resistance from 36 mmHg (IQR 27-46.5 mmHg) and 5.2 Wood Units (WU) (IQR 3.1-5.6 WU) to 28.5 mmHg (IQR 22-35.5 mmHg) and 3.2 WU (IQR 2.4-4.2 WU) (p-values 0.022 and 0.003). More patients were on triple therapy after transition, and side effects reported were less severe., Conclusion: For select patients, transition from a parenteral prostanoid-based therapy to a combination regimen including inhaled treprostinil in the home setting appears safe and well tolerated.

Objective: This study was conducted with the aim of making the contribution to a decision for treatment and determination of the modalities in patients diagnosed with non-Hodgkın lymphoma which increasingly become widespread in the geriatric population., Materials and Methods: Ninety-one patients aged over 65 years diagnosed with lymphoma and treated in Bezmialem Vakıf University Medical Faculty Hospital and Haseki Training and Research Hospital between 2008 and 2013 were retrospectively evaluated. Finally, 63 patients for whom data could be reached were included in the study., Results: Examining the results, histological diagnoses of our patients were as follows: diffuse large B-cell lymphoma (50.8%), follicular lymphoma (23.8%), marginal zone lymphoma (12.7%), mantle cell lymphoma (4.8%), T-cell lymphoma (4.8%), lymphoplasmacytic lymphoma (1.6%) and small lymphocytic lymphoma (1.6%). Stages at the time of diagnosis were early stage by 33.3% and late stage by 66.7%. Of the patients, 36.5% had a low-intermediate and 63.5% a high-intermediate International Prognostic Index score. According to the Eastern Cooperative Oncology Group scoring, 34.9% of the patients have an Eastern Cooperative Oncology Group score of 2-4. Activities of daily living score of 33.3% patients was under 5. Looking at the responses to treatment, the complete response was found in 50.8%, partial response in 4.8%, stable disease in 1.6% and progressive disease in 9.5% of the patients. The mean follow-up duration of patients was found as 25.2 months and disease-free survival after remission as 20.2 months., Conclusion: We found that we have achieved a complete remission in more than half of our patients (50.8%). Based on this, treatment should aim remission in elderly patients.

Background: The DelIVery for Pulmonary Arterial Hypertension clinical trial was a multi-center, prospective, single arm, Investigational Device Exemption study utilizing a fully implantable, programmable intravascular delivery system consisting of a pump and a catheter for intravenous treprostinil. The study met its primary endpoint and demonstrated that the intravascular delivery system significantly reduced catheter related complications at 22,000 subject-days of follow-up compared with a predefined objective performance criterion. Here we summarize the results obtained during a 6.4-year follow-up period., Methods: Throughout study follow-up, participants had clinic visits and medication refills at least every 12 weeks (dependent on the subjects' dose). All adverse events and intravascular delivery system complications were evaluated and recorded., Results: Sixty pulmonary arterial hypertension subjects were followed post device implantation for approximately 282 patient-years (range 87 days to 6.4 years). Of the 60 subjects, 14 died (1 related to intravascular delivery system pump failure), 2 withdrew after lung transplants, and 2 withdrew due to pump pocket infection. No catheter-related bloodstream infections, catheter thrombosis or occlusions, or catheter kinks occurred through 282 patient-years. Two participants had adverse events of abdominal pain, rash, due to subcutaneous treprostinil "leaks" after one catheter puncture and one catheter laceration during pump refill and replacement, respectively. Eight pump failure events occurred: seven pump motor stalls and one early replacement (faulty battery)., Conclusion: Delivery of treprostinil with an intravascular delivery system is a safe alternative to an external delivery system, while providing enhanced life experiences. To preserve the risk-benefit ratio, treatment at specialized pulmonary arterial hypertension centers is recommended until training is disseminated at other sites., (© The Author(s) 2019.)

Rationale: The contributions of diverse cell populations in the human lung to pulmonary fibrosis pathogenesis are poorly understood. Single-cell RNA sequencing can reveal changes within individual cell populations during pulmonary fibrosis that are important for disease pathogenesis. Objectives: To determine whether single-cell RNA sequencing can reveal disease-related heterogeneity within alveolar macrophages, epithelial cells, or other cell types in lung tissue from subjects with pulmonary fibrosis compared with control subjects. Methods: We performed single-cell RNA sequencing on lung tissue obtained from eight transplant donors and eight recipients with pulmonary fibrosis and on one bronchoscopic cryobiospy sample from a patient with idiopathic pulmonary fibrosis. We validated these data using in situ RNA hybridization, immunohistochemistry, and bulk RNA-sequencing on flow-sorted cells from 22 additional subjects. Measurements and Main Results: We identified a distinct, novel population of profibrotic alveolar macrophages exclusively in patients with fibrosis. Within epithelial cells, the expression of genes involved in Wnt secretion and response was restricted to nonoverlapping cells. We identified rare cell populations including airway stem cells and senescent cells emerging during pulmonary fibrosis. We developed a web-based tool to explore these data. Conclusions: We generated a single-cell atlas of pulmonary fibrosis. Using this atlas, we demonstrated heterogeneity within alveolar macrophages and epithelial cells from subjects with pulmonary fibrosis. These results support the feasibility of discovery-based approaches using next-generation sequencing technologies to identify signaling pathways for targeting in the development of personalized therapies for patients with pulmonary fibrosis.

We report the first example of a covalently bound dimer of monolayer protected atomically precise silver nanocluster [Ag25(DMBT)18]- (DMBT stands for 2,4-dimethylbenzenethiol). Covalently linked dimers could be important to design new cluster assembled materials with composite properties.

In this work, we have strategically incorporated a quinoxaline derivative and a diaminomaleonitrile moiety to construct a chemosensor, 2-amino-3-[(quinoxalin-2-ylmethylene)-amino]-but-2-enedinitrile (H2qm). The notable feature of this strategy is to generate a highly conjugated Schiff base platform with interesting binding properties. Remarkably, H2qm exhibited a visual sensing ability towards Cu2+ in 100% aqueous medium. The effectiveness of the chemosensor has been demonstrated by utilizing it to determine the Cu2+ concentration in real samples. Interestingly, the reaction between H2qm and Cu(ClO4)2·6H2O in DMSO yielded a quinoxaline-2-carboxylic acid based compound and single crystal X-ray diffraction analysis unveiled the resulting structure as [(qa)2Cu(H2O)2] (Hqa = quinoxaline-2-carboxylic acid).

A novel chemosensor (H 3 NTS) has been designed for a fast and accurate detection of F - in acetonitrile medium. The UV-Vis, 1 H, 13 C NMR experiments and computational calculations demonstrate that H 3 NTS probe offers a potential colorimetric sensor for discriminating F - among other relevant anions. The detection limit is as low as 6 μM and a reversible colorimetric switch could be devised by sequential addition of F - /Ca 2+ . The promising application of H 3 NTS is also confirmed in real examples where the concentration of F - is a critical parameter, e.g., commercial toothpaste, paper strip and gel form analysis of samples., (Copyright © 2019 Elsevier B.V. All rights reserved.)

An efficient Rh-catalyzed oxidative C-H activation/annulation of 2-arylquinoxalines with internal alkynes is described using Cu(OAc)2·H2O and AgBF4 to afford a diverse variety of substituted quarternary ammonium salts at room temperature. The mechanism of the protocol is established on the basis of isolation of the 5-membered rhodacycle intermediate and kinetic isotope studies. The mild reaction conditions, substrate scope and functional group diversity are the salient practical features.

The synergic property of the CO ligand, in general, can stabilize metal complexes at lower oxidation states. Utilizing this feature of the CO ligand, we have recently isolated and structurally characterized a highly fluxional molybdenum complex [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] (2; Cp* = η 5 -C 5 Me 5 ) comprising the diborane(4) ligand. Compound 2 represents a rare class of bimetallic diborane(4) complex corresponding to a singly bridged C s structure. In an attempt to isolate the tungsten analogue of 2, [{Cp*W(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }], we have isolated a rare vertex-fused cluster, [(Cp*W) 3 WB 9 H 18 ] (5). Having a structural likeness with the dimolybdenum alkyne complex [{CpMo(CO) 2 } 2 C 2 H 2 ], we have further explored the chemistry of 2 with CO gas that yielded a homoleptic trimolybdenum complex, [(Cp*Mo) 3 (μ-H) 2 (μ 3 -H)(μ-CO) 2 B 4 H 4 ] (4). In an attempt to replace the 16-electron {Cp*MoH(CO) 2 } moiety in 4 with isolobal fragment {W(CO) 5 }, we treated the intermediate, obtained from the reaction of Cp*MoCl 4 and LiBH 4 , with the monometal carbonyl fragment {W(CO) 5 ·THF}. The reaction indeed yielded two bimetallic clusters, [(Cp*Mo) 2 B 4 H 8 W(CO) 4 ] (7) and [(Cp*Mo) 2 B 4 H 6 W(CO) 5 ] (8), that seem to have been generated by the replacement of one {BH} or {BH 3 } vertex from [(Cp*Mo) 2 B 5 H 9 ], respectively. All of the compounds have been characterized by various spectroscopic analyses and single-crystal X-ray diffraction studies. Electron-counting rules and molecular orbital analyses provided further insight into the electronic structure of all of these molecules.

We study the effect of impurities on the two types of spin-dimers in the hybrid chain-ladder spin 1/2 quantum magnet SrCuO. Four different impurities were used, namely, the non-magnetic Zn (0.0025 and 0.01 per Cu) and Al (0.0025 and 0.01 per Cu), and magnetic Ni (0.0025 and 0.01 per Cu) and Co (0.01, 0.03, 0.05 and 0.1 per Cu). These impurities were doped in high-quality single-crystals synthesized by the floating-zone method. The magnetic susceptibility of pristine SrCuOis analyzed rigorously to confirm that at low temperatures (K), the 'free' spins in the chains undergo a long-distance dimerization as proposed in a recent study (Sahling et al 2015 Nat. Phys . 11 255). The effect of impurity on these dimers is analyzed by measuring the specific heat down toK. We found that even at the lower impurity concentration, the long-distance dimers are significantly severed but the quantum entangled spin dimerized state of the chains persists. On the other hand, the other type of spin dimers that form at relatively higher temperatures via an intervening Zhang-Rice singlet are found to be practically unaffected at the lower impurity concentration; but at 1% doping these dimers are considerably severed. The effect of Co impurity turned out to be most unusual displaying a strongly anisotropic response, and with a dimerization gap that suppresses faster along the chain/ladder direction than perpendicular to it as a function of increasing Co concentration., (© 2018 IOP Publishing Ltd.)

A facile and reliable method to monitor strongly acidic pH was developed. The sensing mechanism was found to involve the protonation-deprotonation equilibrium of the synthesized probe HQphy (1) (N-phenyl-N'-quinoxalin-2-ylmethylene-hydrazine) within a working range of pH 0.7-2.7. The eventual sensing of Fe3+ was the outcome of acidity imparted by [Fe(H2O)6]3+ ions in solution during the formation of [Fe(H2O)5(OH)]2+. The protonation-deprotonation phenomenon of HQphy was investigated using 1H NMR and single crystal X-ray diffraction experiments. The protonated probe, H2Qphy+, was crystallized with FeCl4-/ClO4- counter anions as [H2Qphy][FeCl4]·H2O (2)/[H2Qphy][ClO4]·H2O (3). A further complex containing the [H2Qphy] cation (4) was also formed. The complexes were characterized by SC-XRD experiments. Moreover, single crystal to single crystal transformation is observed between 1 and 3. In order to understand the sensing mechanism, various analytical studies, such as UV-Vis titration, ESI-MS spectrometry analysis and 1H NMR, were carried out in detail. A theoretical study correlates well with the experimental data, where the π(L) → π*(L) transition of the ligand is red shifted by 100 nm due to protonation of the quinoxaline moiety. The probe enables discrimination of trihalo acetic acid from its mono- and di-analogues.

The reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) 2 } 2 C 2 H 2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) 4 ] fragment, [{Cp*Mo(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (3) was isolated upon treatment with [W(CO) 5 ⋅thf]. Compound 3 shows the intriguing presence of [B 2 H 2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (4) and [{Cp*W(CO) 2 } 2 B 2 H 2 Mo(CO) 4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal-free dioxygenation of alkenes with tert -butyl nitrite and N -hydroxylamines ( N -hydroxyphthalimide, N -hydroxybenzotriazole, and N -hydroxysuccinimide) is described to produce β-aminoxy nitrate esters using air as the oxidant. These organic nitrates can be readily converted into 1,2-diols and 1,2-diketone with broad substrate scope and functional group diversity., Competing Interests: The authors declare no competing financial interest.

Lung transplantation has evolved into a life-saving treatment with improved quality of life for patients with end-stage respiratory failure unresponsive to other medical or surgical interventions. With improving survival rates, the number of lung transplant recipients with preexisting and posttransplant comorbidities that require attention continues to increase. A partnership between transplant and nontransplant care providers is necessary to deliver comprehensive and optimal care for transplant candidates and recipients. The goals of this partnership include timely referral and assistance with transplant evaluation, optimization of comorbidities and preparation for transplantation, management of common posttransplant medical comorbidities, immunization, screening for malignancy, and counseling for a healthy lifestyle to maximize the likelihood of a good outcome. We aim to provide an outline of the main aspects of the care of candidates for and recipients of lung transplants for nontransplant physicians and other care providers., (Copyright © 2016. Published by Elsevier Inc.)

Iron-catalyzed dioxygenation of alkenes in air using N-hydroxyphthalimide (NHPI) and N-hydroxybenzotriazole (HOBt) is described at room temperature. The products can be readily converted into 1,2-vicinal diols using PPh3 and Mo(CO)6. The use of Fe(NO3)3·9H2O as the catalyst, mild reaction conditions and the selectivity are the significant practical features. The radical scavenger experiment suggests that the reaction proceeds via a radical intermediate. The synthetic and mechanistic aspects have been presented.

Vanadium-catalyzed C-N dehydrogenative cross-coupling of alkenyl hydrazones leading to functionalized pyrazoles is described in a 1:1 mixture of toluene/H2O using air as the terminal oxidant. Significant practical features include use of the commercial nontoxic VOSO4 as a recyclable catalyst, mild reaction conditions, scalability, and the broad substrate scope. Some of the product pyrazoles exhibit interesting photophysical properties. Fluorescence light-up sensing of BSA protein by one of the pyrazoles is also highlighted.

Iron(III)-mediated radical nitration of bisarylsulfonyl hydrazones is described. In this protocol, the nontoxic and inexpensive Fe(NO3)3·9H2O plays a dual role as catalyst as well as nitro source. The mild conditions, broad substrate scope, and the functional group compatibility are the significant features. The reaction pathway has been demonstrated using DFT calculations, and the products can be subsequently converted into oximes using SnCl2·2H2O in high yields.