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Objectives: The aim of the study was to analyze the data of diabetic patients regarding warning signs of hypoglycemia to predict it at an early stage using various novel machine learning (ML) algorithms. Individual interviews with diabetic patients were conducted over 6 months to acquire information regarding their experience with hypoglycemic episodes., Design: This information included warning signs of hypoglycemia, such as incoherent speech, exhaustion, weakness, and other clinically relevant cases of low blood sugar. Researchers used supervised, unsupervised, and hybrid techniques. In supervised techniques, researchers applied regression, while in hybrid classification ML techniques were used. In a 5-fold cross-validation approach, the prediction performance of seven models was examined using the area under the receiver operating characteristic curve (AUROC). We analyzed the data of 290 diabetic patients with low blood sugar episodes., Results: Our investigation discovered that gradient boosting and neural networks performed better in regression, with accuracies of 0.416 and 0.417, respectively. In classification models, gradient boosting, AdaBoost, and random forest performed better overall, with AUC scores of 0.821, 0.814, and 0.821, individually. Precision values were 0.779, 0.775, and 0.776 for gradient boosting, AdaBoost, and random forest, respectively., Conclusion: AdaBoost and Gradient Boosting models, in particular, outperformed all others in predicting the probability of clinically severe hypoglycemia. These techniques enable community health nurses to predict hypoglycemia at an early stage and provide the necessary therapies to patients to prevent complications resulting from hypoglycemia., (© 2024 Wiley Periodicals LLC.)

Enzymes of the ureohydrolase superfamily are specific in recognizing their substrates. While looking to broaden the substrate specificity of 4-guanidinobutyrase (GBase), we isolated a yeast, typed as Candida parapsilosis (NCIM 3689), that efficiently utilized both 4-guanidinobutyrate (GB) and 3-guanidinopropionate (GP) as a sole source of nitrogen. A putative GBase sequence was identified from its genome upon pBLAST query using the GBase sequence from Aspergillus niger (AnGBase). The C. parapsilosis GBase (CpGBase) ORF was PCR amplified, cloned, and sequenced. Further, the functional CpGBase protein expressed in Saccharomyces cerevisiae functioned as GBase and 3-guanidinopropionase (GPase). S. cerevisiae cannot grow on GB or GP. However, the transformants expressing CpGBase acquired the ability to utilize and grow on both GB and GP. The expressed CpGBase protein was enriched and analyzed for substrate saturation and product inhibition by γ-aminobutyric acid and β-alanine. In contrast to the well-characterized AnGBase, CpGBase from C. parapsilosis is a novel ureohydrolase and showed hyperbolic saturation for GB and GP with comparable efficiency (Vmax/KM values of 3.4 and 2.0, respectively). With the paucity of structural information and limited active site data available on ureohydrolases, CpGBase offers an excellent paradigm to explore this class of enzymes., (© The Author(s) 2024. Published by Oxford University Press on behalf of FEMS.)

Objective: Human papillomavirus and other predicting factors are responsible causing cervical cancer, and early prediction and diagnosis is the solution for preventing this condition.  The objective is to find out and analyze the predictors of cervical cancer and to study the issues of unbalanced datasets using various Machine Learning (ML) algorithm-based models., Methods: A multi-stage sampling strategy was used to recruit 501 samples for the study. The educational intervention was the video-assisted counseling which is consisted of two educational methods: a documentary film and face-to- face interaction with women followed by reminders. Following the collection of baseline data from these subjects, they were encouraged to undergo Pap smear screening. Women having abnormal Pap tests were sent for biopsy. Machine learning classification methods such as Decision Tree (DT), Random Forest (RF), Logistic Regression (LR), Multi-layer Perceptron (MLP) and Naive Bayes(NB) were used to evaluate the unbalanced input and target datasets., Result: Merely 398 women out of 501 showed an interest to participate in the study, but only 298 stated a willingness for cervical screening. Atypical malignant cells were discovered on the cervix of 26 women who had abnormal pap tests. These women had guided for further tests, such as a cervical biopsy, and seven women had been diagnosed with cervical cancer. LR in models 1, 2, and 4 showed 88% to 94% sensitivity with 84% to 89% accuracy, respectively for cervical cancer prediction, whereas DT in models 3, 5, and 6 algorithms exhibited 83% to 84% sensitivity with 84% to 88% accuracy, respectively. The NB and LR algorithms produced the highest area under the ROC curve for testing dataset, but all models performed similarly for training data., Conclusion: In current study , Logistic Regression and Decision Tree algorithms were identified as the best-performed ML algorithm classifiers to detect the significant predictors.

Catalyst design for ethylene oligomerization has attracted significant interest. Herein, we report the synthesis of phosphine-sulfonamide-derived palladium complexes and examine their performance in ethylene oligomerization. Arresting a dilithiation intermediate of N-(2-bromophenyl)-4-methylbenzenesulfonamide (1) at -84 °C selectively produced N-(2-(bis(2-methoxyphenyl)phosphanyl)phenyl)-4-methylbenzenesulfonamide (L1A). However, the same reaction at -41 °C delivered a different ligand; 2-(bis(2-methoxyphenyl)phosphanyl)-4-methyl-N-phenylbenzenesulfonamide (L2A). The generality of our strategy has been demonstrated by preparing N-(2-(diphenylphosphanyl)phenyl)-4-methylbenzenesulfonamide (L1B) and 2-(diphenylphosphanyl)-4-methyl-N-phenylbenzenesulfonamide (L2B). Subsequently, L1A and L1B were treated with a palladium precursor to yield 5-membered complexes C1 and C2, respectively. In contrast, L2A upon treatment with palladium produced a 6-membered metal complex C3. Thus, a small library of 7 palladium complexes (C1-C7) were synthesized by varying the donor moiety (pyridine, DMSO, and acetonitrile). The identity of palladium complexes was unambiguously ascertained using a combination of spectroscopic and analytical methods, including single-crystal X-ray diffraction. The performance of the complexes C1-C7 was investigated in ethylene oligomerization and almost all of them were found to be active. The resultant ethylene oligomers were characterized using 1H and 13C NMR, MALDI-ToF-MS, and GPC. Detailed screening of reaction parameters revealed 100 °C and 40 bars ethylene to be optimal conditions. Complex C5 outperformed other complexes and produced ethylene oligomers with a molecular weight of 1000-1900 g mol-1.

In the search for optimal platforms for protein expression and secretion, filamentous fungi in principle provide some of the best microbial cell factories. They are inherently endowed with the ability to secrete proteins. Fungi belonging to Aspergillus and Trichoderma species are well-studied for industrial production of proteins and enzymes. Our understanding of these organisms at the level of transcription, translation, post-translational processing and the secretory pathways has improved significantly in recent years. Despite this, the ability of these fungal secretion platforms has not yet been able to match their intrinsic secretion capacity to produce foreign proteins. Details of the molecular mechanisms of the secretory pathways in filamentous fungi are emerging. This knowledge can be gainfully employed to enhance protein production in filamentous fungi, particularly in the secretion of heterologous proteins of value.

Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [{P∧O}PdMe(L)] (P∧O=κ 2 -P,O-Ar 2 PC 6 H 4 SO 2 O with Ar=2-MeOC 6 H 4 ; L=C 2 H 6 OS) and the existence of respective insertion intermediates in moderate yield (up to 37 %) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Designing co-catalyst-free late transition metal complexes for ethylene polymerization is a challenging task at the interface of organometallic and polymer chemistry. Herein, a set of new, co-catalyst-free, single-component catalytic systems for ethylene polymerization have been unraveled. Treatment of anthranilic acid with various aldehydes produced four iminocarboxylate ligands (L1-L4) in very good to excellent yield (75-92 %). The existence of 2-((2-methoxybenzylidene)amino) benzoic acid (L1) has been unambiguously demonstrated using NMR spectroscopy, MS and single-crystal X-ray diffraction. A neutral Pd-iminocarboxylate complex [{N O}PdMe(L1)] (N O=κ 2 -N,O-ArCHNC 6 H 4 CO 2 with Ar=2-MeOC 6 H 4 ) C1 was prepared by treating stoichiometric amount of L1.Na with palladium precursor. The identity of C1 was confirmed by 1-2D NMR spectroscopy and single-crystal X-ray diffraction studies. Along the same lines, palladium complexes C2-C4 were prepared from ligands L2-L4 respectively. In-situ high-pressure NMR investigations revealed that these Pd complexes are amenable to ethylene insertion and undergo facile β-H elimination to produce propylene. These palladium complexes were then evaluated in ethylene polymerization reaction and various reaction parameters were screened. When C1-C4 were exposed to ethylene pressures of 10-50 bar, formation of low-molecular-weight polyethylene was observed., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A reaction between sodium 2-formylbenzenesulfonate and aniline revealed the near-quantitative (91%) formation of sodium-2-((phenylimino)methyl)benzenesulfonate L1 . The identity of L1 was unambiguously ascertained using spectroscopic and analytical methods. The scope of this methodology was widened and various electron-donating amines were treated with sodium 2-formylbenzenesulfonate, and a small library of 6 imine ligands L2-L6 was generated. When L2 was treated with [(COD)PdMeCl], instead of the anticipated [ L2 PdMe(DMSO)] complex, the formation of [(DMSO) 2 Pd 2 Cl 2 Me 2 ] Pd-Dim was observed. Nevertheless, the desired imino-methyl benzenesulfonate-ligated palladium complex [ L2 PdMe(Lu)] C1 was obtained by in situ abstraction of chloride and addition of bulky 2,6-lutidine as the donor group. The observation of characteristic Pd-Me protons at 0.06 ppm and the corresponding carbon at -8.1 ppm indicated the formation of C1 . These 1D NMR observations were corroborated by 2D C-H correlation spectra and mass analysis, and the existence of C1 was unambiguously ascertained. Along the same lines, L4 and L5 were treated with a palladium precursor to produce [ L4/5 PdMe(Lu)]-type complexes C2-C3 in 55-84% yield, and their identity was established by using a combination of spectroscopic tools, analytical methods, and single-crystal X-ray diffraction. The synthetic utility of C1-C3 has been demonstrated by utilizing these complexes in the insertion polymerization of ethylene to polyethylene., Competing Interests: The authors declare no competing financial interest.

Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC 6 H 4 NH(CO)NH 2 }{Ph 2 PC 6 H 4 NH(CO)NH 2 }PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC 6 H 4 NH(CO)NHPh}{Ph 2 PC 6 H 4 NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 °C.

Psyllium is widely used as a medicinally active natural polysaccharide for treating conditions like constipation, diarrhea, and irritable bowel syndrome, inflammatory bowel disease, ulcerative colitis and colon cancer. Studies have been performed to characterize and modify the polysaccharide obtained from psyllium seed husk and to evaluate its use as a pharmaceutical excipient, but no studies have been performed to evaluate the properties of the polysaccharide present in psyllium seeds. The present study focuses on phosphorylation of psyllium seed polysaccharide (PPS) using sodium tri-meta phosphate as the cross-linking agent. The modified phosphorylated psyllium seed polysaccharide was then evaluated for physicochemical properties, rheological properties, spectral analysis, thermal analysis, crosslinking density and acute oral toxicity studies. The modified polysaccharide (PhPPS) has a high swelling index due to which it can be categorized as a hydrogel. The percent increase in swelling of PhPPS as compared to PPS was found to be 90.26%. The PPS & PhPPS mucilages of all strengths were found to have shear thinning properties. These findings are suggestive of the potential use of PhPPS as gelling & suspending agent. PhPPS was found to have a mucoadhesive property which was comparable with carbopol., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A single-step synthesis, structural characterization and application of a neutral, acetonitrile ligated, palladium-phosphinesulfonate complex [{P ∧ O}PdMe(L)] (P ∧ O = κ 2 -P,O-Ar 2 P C 6 H 4 SO 2 O with Ar = 2-MeOC 6 H 4 ; L = CH 3 CN) ( 3 ) in coordination/insertion copolymerization of ethylene with difunctional olefin is investigated. In a significant development, complex 3 was found to catalyze insertion copolymerization of industrially relevant 1,1-disubstituted difunctional vinyl monomers for the first time. Thus, insertion copolymerization of ethyl-2-cyanoacrylate (ECA or super glue) and trifluoromethyl acrylic acid (TFMAA) with ethylene produced the corresponding copolymers with 6.5% ECA and 3% TFMAA incorporation. Increasing the concentration of difunctional olefins led to higher incorporation but at the expense of lower activities. These observations indicate that complex 3 tolerates difunctional vinyl monomers and provides direct access to difunctional polyolefins that have not been attempted before.

Cells often respond to diverse environmental stresses by inducing stress granules (SGs) as an adaptive mechanism. SGs are generally assembled as a result of aggregation of mRNAs stalled in a translational pre-initiation complex, mediated by a set of RNA-binding proteins such as G3BP and TIA-1. SGs may serve as triage centres for storage, translation re-initiation or degradation of specific mRNAs. However, the mechanism involved in the modulation of their assembly/disassembly is unclear. Here we report that Wnt signalling negatively regulates SG assembly through Dishevelled (Dvl), a cytoplasmic Wnt effector. Overexpression of Dvl2, an isoform of Dvl, leads to impairment of SG assembly through a DEP domain dependent mechanism. Intriguingly, the Dvl2 mutant K446M, which corresponds to an analogous mutation in Drosophila Dishevelled DEP domain (dsh(1)) that results in defective PCP pathway, fails to antagonize SG assembly. Furthermore, we show that Dvl2 exerts the antagonistic effect on SG assembly through a mechanism involving Rac1-mediated inhibition of RhoA. Dvl2 interacts with G3BP, a downstream component of Ras signalling involved in SG assembly, and functional analysis suggests a model wherein the Dvl-Rac1-RhoA axis regulates G3BP's SG-nucleating activity. Collectively, these results define an antagonistic effect of Wnt signalling on SG assembly, and reveal a novel role for Wnt/Dvl pathway in the modulation of mRNA functions.

Seasonal patterns of temperature, pH, conductivity dissolved oxygen, phosphate and sulphate have been studied on the basis of physico-chemical characteristics of pond ecosystem. Importance of soil egg banks and their contribution to the diversity in freshwater ecosystem has been studied. We have focussed our attention on soil egg bank diversity and zooplankton emergence patterns of some recently dried aquatic habitats, comparing to that of neighbouring temporary pools with the permanent ponds. The emergence pattern from the soil egg bank followed an orderly succession from Protists-Rotifers and Crustaceans have been investigated. Dominant Protists emerged from the egg bank were Lacrymaria within rotifers. They were the first to emerge followed by Hexarthra blooms. The diversity of zooplankton in permanent ponds was significantly higher (i.e., 19) than the diversity in the ephemeral pools (i.e., 08). However; the zooplankton abundance in the ephemeral pools was higher with more than an order of magnitude, than that in ponds. Interestingly the number of species recorded in the egg bank was more than those present in the water columns of the pools. We have recorded 08 species of rotifera i.e. Lecane sp L curvicornis, L. bulla, K. quadrata, B. patulus, B. rubens, Branchionus calyciflorus, Testudinella sp which were not present in the neighboring permanent or ephemeral waterbodies during that period. Unequivocally suggest that in order to understand the zooplankton biodiversity; it is also important to evaluate the diversity of egg bank present in the sediment. A total 19 species were recorded including Copepoda 06 sp, Cladocera 05 sp and Rotifera 08 sp.