One-Pot Manganese (I)-Catalyzed Oxidant-Controlled Divergent Functionalization of 2-Arylindazoles.

The oxidant-controlled divergent synthesis of C-2' formyl 2H-indazoles and indazoloindazolediones has been developed through Mn(I)- catalyzed ortho C-H functionalization of 2H-indazoles with para-formaldehyde to afford C-2' hydroxymethylated 2H-indazoles and subsequently oxidation with varying the amount of DDQ in one-pot. By employing selectfluor as the oxidant instead of DDQ, this reaction exclusively provided indazolebenzoxazine derivatives. This strategy delivered unsymmetrical indazoloindazoledione and indazolobenzoxazine with varied functional group tolerance in moderate to good yields.

Kinetic Models of Wealth Distribution with Extreme Inequality: Numerical Study of Their Stability against Random Exchanges.

In view of some recent reports on global wealth inequality, where a small number (often a handful) of people own more wealth than 50% of the world's population, we explored if kinetic exchange models of markets could ever capture features where a significant fraction of wealth can concentrate in the hands of a few as the market size N approaches infinity. One existing example of such a kinetic exchange model is the Chakraborti or Yard-Sale model; in the absence of tax redistribution, etc., all wealth ultimately condenses into the hands of a single individual (for any value of N), and the market dynamics stop. With tax redistribution, etc., steady-state dynamics are shown to have remarkable applicability in many cases in our extremely unequal world. We show that another kinetic exchange model (called the Banerjee model) has intriguing intrinsic dynamics, where only ten rich traders or agents possess about 99.98% of the total wealth in the steady state (without any tax, etc., like external manipulation) for any large N value. We will discuss the statistical features of this model using Monte Carlo simulations. We will also demonstrate that if each trader has a non-zero probability f of engaging in random exchanges, then these condensations of wealth (e.g., 100% in the hand of one agent in the Chakraborti model, or about 99.98% in the hands of ten agents in the Banerjee model) disappear in the large N limit. Moreover, due to the built-in possibility of random exchange dynamics in the earlier proposed Goswami-Sen model, where the exchange probability decreases with the inverse power of the wealth difference between trading pairs, one does not see any wealth condensation phenomena. In this paper, we explore these aspects of statistics of these intriguing models.

Sandpile Universality in Social Inequality: Gini and Kolkata Measures.

Social inequalities are ubiquitous and evolve towards a universal limit. Herein, we extensively review the values of inequality measures, namely the Gini (g) index and the Kolkata (k) index, two standard measures of inequality used in the analysis of various social sectors through data analysis. The Kolkata index, denoted as k, indicates the proportion of the 'wealth' owned by (1-k) fraction of the 'people'. Our findings suggest that both the Gini index and the Kolkata index tend to converge to similar values (around g=k≈0.87, starting from the point of perfect equality, where g=0 and k=0.5) as competition increases in different social institutions, such as markets, movies, elections, universities, prize winning, battle fields, sports (Olympics), etc., under conditions of unrestricted competition (no social welfare or support mechanism). In this review, we present the concept of a generalized form of Pareto's 80/20 law (k=0.80), where the coincidence of inequality indices is observed. The observation of this coincidence is consistent with the precursor values of the g and k indices for the self-organized critical (SOC) state in self-tuned physical systems such as sand piles. These results provide quantitative support for the view that interacting socioeconomic systems can be understood within the framework of SOC, which has been hypothesized for many years. These findings suggest that the SOC model can be extended to capture the dynamics of complex socioeconomic systems and help us better understand their behavior.

Microscopic and Transcriptomic Analyses of Dalbergoid Legume Peanut Reveal a Divergent Evolution Leading to Nod-Factor-Dependent Epidermal Crack-Entry and Terminal Bacteroid Differentiation.

Root nodule symbiosis (RNS) is the pillar behind sustainable agriculture and plays a pivotal role in the environmental nitrogen cycle. Most of the genetic, molecular, and cell-biological knowledge on RNS comes from model legumes that exhibit a root-hair mode of bacterial infection, in contrast to the Dalbergoid legumes exhibiting crack-entry of rhizobia. As a step toward understanding this important group of legumes, we have combined microscopic analysis and temporal transcriptome to obtain a dynamic view of plant gene expression during Arachis hypogaea (peanut) nodule development. We generated comprehensive transcriptome data by mapping the reads to A. hypogaea, and two diploid progenitor genomes. Additionally, we performed BLAST searches to identify nodule-induced yet-to-be annotated peanut genes. Comparison between peanut, Medicago truncatula, Lotus japonicus, and Glycine max showed upregulation of 61 peanut orthologs among 111 tested known RNS-related genes, indicating conservation in mechanisms of nodule development among members of the Papilionoid family. Unlike model legumes, recruitment of class 1 phytoglobin-derived symbiotic hemoglobin (SymH) in peanut indicates diversification of oxygen-scavenging mechanisms in the Papilionoid family. Finally, the absence of cysteine-rich motif-1-containing nodule-specific cysteine-rich peptide (NCR) genes but the recruitment of defensin-like NCRs suggest a diverse molecular mechanism of terminal bacteroid differentiation. In summary, our work describes genetic conservation and diversification in legume-rhizobia symbiosis in the Papilionoid family, as well as among members of the Dalbergoid legumes.[Formula: see text] Copyright © 2022 The Author(s). This is an open access article distributed under the CC BY-NC-ND 4.0 International license.

Organocatalytic Oxidative C-H Amination of Aldehyde Hydrazones with Azoles at Ambient Temperature.

An efficient, metal-free, and direct oxidative amination of aldehyde-derived hydrazones with azoles has been developed using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as an organocatalyst at ambient temperature. This protocol provides a wide range of aminated hydrazone derivatives in a step and atom economical fashion. The reaction possibly follows a radical mechanism.

Kinetic exchange income distribution models with saving propensities: inequality indices and self-organized poverty level.

We report the numerical results for the steady-state income or wealth distribution [Formula: see text] and the resulting inequality measures (Gini [Formula: see text] and Kolkata [Formula: see text] indices) in the kinetic exchange models of market dynamics. We study the variations of [Formula: see text] and of the indices [Formula: see text] and [Formula: see text] with the saving propensity [Formula: see text] of the agents, with two different kinds of trade (kinetic exchange) dynamics. In the first case, the exchange occurs between randomly chosen pairs of agents and in the next, one of the agents in the chosen pair is the poorest of all and the other agent is randomly picked up from the rest of the population (where, in the steady state, a self-organized poverty level or SOPL appears). These studies have also been made for two different kinds of saving behaviours. One, where each agent has the same value of [Formula: see text] (constant over time) and the other where [Formula: see text] for each agent can take two values (0 and 1), changing randomly over a fraction of time [Formula: see text] of choosing [Formula: see text]. We find that the inequality decreases with increasing savings ([Formula: see text]); inequality indices ([Formula: see text] and [Formula: see text]) decrease and SOPL increases with increasing [Formula: see text], indicating possible applications in economic policy making. This article is part of the theme issue 'Kinetic exchange models of societies and economies'.

Study of COVID-19 epidemiological evolution in India with a multi-wave SIR model.

The global pandemic due to the outbreak of COVID-19 ravages the whole world for more than two years in which all the countries are suffering a lot since December 2019. In this article characteristics of a multi-wave SIR model have been studied which successfully explains the features of this pandemic waves in India. Origin of the multi-wave pattern in the solution of this model is explained. Stability of this model has been studied by identifying the equilibrium points as well as by finding the eigenvalues of the corresponding Jacobian matrices. In this model, a finite probability of the recovered people for becoming susceptible again is introduced which is found crucial for obtaining the oscillatory solution in other words. Which on the other hand incorporates the effect of new variants, like delta, omicron, etc in addition to the SARS-CoV-2 virus. The set of differential equations has been solved numerically in order to obtain the variation of susceptible, infected and removed populations with time. In this phenomenological study, some specific sets of parameters are chosen in order to explain the nonperiodic variation of infected population which is found necessary to capture the feature of epidemiological wave prevailing in India. The numerical estimations are compared with the actual cases along with the analytic results.

Rhodium-Catalyzed Directed C(sp2)-H Bond Addition of 2-Arylindazoles to N-Sulfonylformaldimines and Activated Aldehydes.

Rhodium-catalyzed directed C-H functionalization of 2-arylindazoles with N-sulfonylformaldimines has been developed to provide a variety of N-benzylarylsulfonamide derivatives with good to excellent yields. Different activated aldehydes like ethyl glyoxalate and 2,2,2-trifluoroacetaldehyde also efficiently underwent nucleophilic addition with 2-arylindazoles. These selective transformations occur through the control of C3 nucleophilicity of indazole moiety. Mechanistic studies suggest that C-H activation step may be a rate-limiting step.

Regioselective hydroarylation and arylation of maleimides with indazoles via a Rh(iii)-catalyzed C-H activation.

Switchable Rh(iii)-catalyzed highly regioselective hydroarylation and oxidative arylation of maleimides with 2-arylindazoles via C-H activation have been demonstrated. The reaction affords 3-(2-(2H-indazol-2-yl)phenyl)succinimide and 3-(2-(2H-indazol-2-yl)phenyl)maleimide derivatives in high yields with wide functional group tolerance. A mechanistic study was performed to depict C-H bond cleavage that might be involved in the turnover limiting step.

Fe(iii)-Catalyzed synthesis of steroidal imidazoheterocycles as potent antiproliferative agents.

An efficient and practical method has been developed for the synthesis of steroidal imidazoheterocycles via cost-effective and environmentally benign FeCl3-catalyzed oxidative amination. A library of steroidal imidazo[1,2-a]pyridines was directly synthesized from readily available 2-aminopyridines and steroidal ketones in aerobic conditions. The synthesized compounds were screened for activity on human microsomal cytochrome P450s CYP7, CYP17 and CYP21. Antiproliferative activity of two lead compounds 3ia and 3la was additionally evaluated against the human MCF-7 (breast cancer), SKOV3 (ovarian cancer), and 22Rv1 (prostate cancer) cell lines. Steroidal imidazo[1,2-a]pyridine 3la which is a substrate molecule for CYP17A1 with IC50 = 1.7 µM (MCF-7), 3.0 (SKOV3), and 6.0 µM (22Rv1) has proved to be more active than reference drug cisplatin.

Efficacy of combination therapy of inositols, antioxidants and vitamins in obese and non-obese women with polycystic ovary syndrome: an observational study.

Polycystic ovarian syndrome (PCOS) is one of the most common endocrine disorders in women of both developed and developing countries. It is associated with insulin resistance, hyperinsulinemia, hyperandrogenism, oxidative stress and various long-term complications. The present study was undertaken to evaluate the efficacy and safety of the supplementation (Trazer F ForteTM-CORONA Remedies Pvt. Ltd.) providing combination of insulin sensitising agents (myo-inositol, D-chiro-inositol and chromium picolinate), antioxidants (N-acetylcysteine and lycopene) and vitamins (vitamin D, biotin and folic acid) in women with PCOS. After 12 weeks of supplementation, a significant improvement was observed in menstrual cyclicity, acne and hirsutism in both obese and lean PCOS patients. A significant reduction was observed in body weight and BMI of obese subjects. However, both parameters remain unchanged in lean subjects. We suggest that combination therapy of insulin sensitising agents, antioxidants and vitamins may be a fruitful approach for the management of PCOS.Impact statementWhat is already known on this subject? Monotherapy of insulin sensitising agents, antioxidants and vitamins is beneficial in the treatment of PCOS.What do the results of this study add? Combined use of insulin sensitising agents (myo-inositol, D-chiro-inositol and chromium picolinate), antioxidants (N-acetylcysteine and lycopene), and vitamins (vitamin D, biotin and folic acid) is safe and effective in obese and non-obese women with PCOS.What are the implications of these findings for clinical practice and/or further research? Since PCOS is a multifactorial and a complex endocrine disorder, combination therapy can be used for the comprehensive management of PCOS.

Tracking urban human activity from mobile phone calling patterns.

Timings of human activities are marked by circadian clocks which in turn are entrained to different environmental signals. In an urban environment the presence of artificial lighting and various social cues tend to disrupt the natural entrainment with the sunlight. However, it is not completely understood to what extent this is the case. Here we exploit the large-scale data analysis techniques to study the mobile phone calling activity of people in large cities to infer the dynamics of urban daily rhythms. From the calling patterns of about 1,000,000 users spread over different cities but lying inside the same time-zone, we show that the onset and termination of the calling activity synchronizes with the east-west progression of the sun. We also find that the onset and termination of the calling activity of users follows a yearly dynamics, varying across seasons, and that its timings are entrained to solar midnight. Furthermore, we show that the average mid-sleep time of people living in urban areas depends on the age and gender of each cohort as a result of biological and social factors.

Magnetic phases of XY model with three-spin terms: interplay of topology and entanglement.

Magnetic and topological properties along with quantum correlations in terms of several entanglement measures have been investigated for an antiferromagnetic (AFM) spin-1/2 XY model in the presence of transverse magnetic field and XZX-YZY type of three-spin interactions. Symmetries of the spin Hamiltonian have been identified. Under the Jordan-Wigner transformation, the spin Hamiltonian converted into spinless superconducting model with nearest neighbor (NN) hopping and Cooper pairing terms in addition to next NN Cooper pairing potential. Long range AFM order has been studied in terms of staggered spin-spin correlation functions, while the topological orders have been characterized by winding numbers. Magnetic and topological phase diagrams have been prepared. Faithful coexistence of magnetic and topological superconducting phases is found in the entire parameter regime. Boundaries of various quantum phases have been marked and positions of bicritical points have been identified.

Q factor: A measure of competition between the topper and the average in percolation and in self-organized criticality.

We define the Q factor in the percolation problem as the quotient of the size of the largest cluster and the average size of all clusters. As the occupation probability p is increased, the Q factor for the system size L grows systematically to its maximum value Q_{max}(L) at a specific value p_{max}(L) and then gradually decays. Our numerical study of site percolation problems on the square, triangular, and simple cubic lattices exhibits that the asymptotic values of p_{max}, though close, are distinct from the corresponding percolation thresholds of these lattices. We also show, using scaling analysis, that at p_{max} the value of Q_{max}(L) diverges as L^{d} (d denoting the dimension of the lattice) as the system size approaches its asymptotic limit. We further extend this idea to nonequilibrium systems such as the sandpile model of self-organized criticality. Here the Q(ρ,L) factor is the quotient of the size of the largest avalanche and the cumulative average of the sizes of all the avalanches, with ρ the drop density of the driving mechanism. This study was prompted by some observations in sociophysics.

Comparative study of the outcomes of newly developed polypropylene-based modified trabeculectomy and glaucoma shunt surgery in neovascular glaucoma.

BACKGROUND: Neovascular glaucoma (NVG) is a secondary glaucoma with a poor visual prognosis. Trabeculectomy with antifibrotic agents, glaucoma drainage devices (GDDs), and cyclo-destructive procedures are recommended in patients who are refractory to medical management. However, due to the poor success rate of conventional trabeculectomy and the higher cost of GDDs, alternative procedures need to be looked at. PURPOSE: To compare the surgical outcomes and economic aspects of a newly developed polypropylene suture bed-based modified trabeculectomy to Ahmed glaucoma valve (AGV) implantation for NVG. METHODS: It was a prospective interventional study conducted at a tertiary care center between 2018 and 2020. Consecutive patients with NVG with a minimum follow-up of 18 months were included. Surgical outcomes are mainly based on intraocular pressure (IOP) control and the cost of surgery. RESULTS: Sixty eyes were included out of which 40 (60.6%) underwent modified trabeculectomy and 20 (33.7%) underwent AGV. At the final follow-up, no significant difference (P < 0.05) was found between the surgical outcomes of both groups. The complete success rate (IOP < 21 mm Hg without antiglaucoma medications) was 60 and 65% while the qualified success rate (IOP < 21 mm Hg with antiglaucoma medications) was 30 and 25% in modified trabeculectomy and AGV groups, respectively, at final follow-up. The cost of surgery was significantly higher in the AGV group (P < 0.0001). CONCLUSION: Modified trabeculectomy as described might be a better alternative for NVG eyes.

Efficacy, Safety and Immunogenicity of Sun's Ranibizumab Biosimilar in Neovascular Age-Related Macular Degeneration: A Phase 3, Double-Blind Comparative Study.

INTRODUCTION: The study aimed to evaluate comparability in terms of efficacy, safety and immunogenicity of Sun's ranibizumab biosimilar with reference ranibizumab in patients with neovascular age-related macular degeneration (nAMD). METHODS: This prospective, randomised, double-blind, two-group, parallel-arm, multicentre, phase 3 comparative study included patients with nAMD ≥ 50 years, randomised (in a 2:1 ratio) in a double-blind manner to receive 0.5 mg (0.05 mL) intravitreal injection of either Sun's ranibizumab or reference ranibizumab in the study eye every 4 weeks until week 16 (total of four doses). RESULTS: Primary endpoint results demonstrated equivalence in the proportion of patients who lost fewer than 15 letters from baseline best-corrected visual acuity (BCVA) to the end of week 16 (99% of patients in Sun's ranibizumab and 100% in reference ranibizumab; p > 0.9999), with the proportional difference (90% confidence interval) at -1% (-2.51, +0.61) lying within a pre-specified equivalence margin. Visual acuity improved by 15 or more letters in 43% of Sun's ranibizumab group and 37% of the reference ranibizumab group (p = 0.4267). The mean increase in BCVA was 15.7 letters in Sun's ranibizumab group and 14.6 letters in the reference ranibizumab group (p < 0.001 within both groups and p = 0.5275 between groups). The mean change in central macular thickness was comparable between groups (p = 0.7946). Anti-ranibizumab antibodies were found in one patient of the reference ranibizumab group, while neutralising antibodies were not found in any patients. Both products were well tolerated. CONCLUSION: Sun's ranibizumab biosimilar is found to be therapeutically equivalent to reference ranibizumab in patients with nAMD. There were no additional safety or immunogenicity concerns. TRIAL REGISTRATION: CTRI/2020/09/027629, registered on 07 September 2020.

Topological phases of monolayer and bilayer depleted Lieb lattices.

Existence of nontrivial topological phases in a tight binding Haldane-like model on the depleted Lieb lattice is reported. This two-band model is formulated by considering the nearest-neighbor (NN), next-NN (NNN) and next-NNN hopping terms along with complex phase which breaks the time reversal symmetry of this semi-metallic system. Topological feature of this model is studied along with the presence of sublattice symmetry breaking staggered onsite energy. Combined effect of these two broken symmetries is found crucial for an additional transition between nontrivial and trivial phases. System exhibits two types of phase transitions, say, between two nontrivial phases and nontrivial to trivial phases. Nonzero Chern numbers, existence of Hall plateau and symmetry protected edge states confirm the presence of the nontrivial phases. This two-band system hosts four different types of phases where two are topological. Additionally topological properties of stacked bilayer of the depleted Lieb lattices is also studied with similar Haldane-like Hamiltonian. This four-band system is found to host Chern insulating phases, with higher values of Chern numbers supported by in-gap edge states.

Engineering topological phases of any winding and Chern numbers in extended Su-Schrieffer-Heeger models.

Simple route of engineering topological phases for any desired value of winding and Chern numbers is found in the Su-Schrieffer-Heeger (SSH) model by adding a further neighbor hopping term of varying distances. It is known that the standard SSH model yields a single topological phase with winding number,ν = 1. In this study it is shown that how one can generate topological phases with any values of winding numbers, for examples,ν=±1,±2,±3,…,in the presence of a single further neighbor term which preserves inversion, particle-hole and chiral symmetries. Quench dynamics of the topological and trivial phases are studied in the presence of a specific nonlinear term. Another version of SSH model with additional modulating nearest neighbor and next-nearest-neighbor hopping parameters was introduced before which exhibit a single topological phase characterized by Chern number,C=±1. Standard form of inversion, particle-hole and chiral symmetries are broken in this model. Here this model has been studied in the presence of several types of parametrization among which, for a special case the system is found to yield a series of phases with Chern numbers,C=±1,±2,±3,….In another parametrization, multiple crossings within the edge states energy lines are found in both trivial and topological phases. Topological phase diagrams are drawn for every case. Emergence of spurious topological phases is also reported.

A Prospective Observational Study on Changes in Intraocular Pressure and Iridocorneal Angle Following the Use of Escitalopram and Amitriptyline.

Background: Depression has emerged as one of the prime morbidities affecting professional and personal lives worldwide. Antidepressants are one of the mainstays of management of depressive episodes. Although antidepressants are considered a safe class of drugs, the studies examining the effects of antidepressant prescription on intraocular pressure (IOP) have shown a propensity to increase IOP, but not consistently. This study aimed to compare the changes in IOP and iridocorneal angle in drug-naïve patients with depressive episodes prescribed escitalopram or amitriptyline. Methods: Overall, 109 patients were recruited, of which 53 were prescribed amitriptyline and 56, escitalopram. A comparison of IOP and the iridocorneal angle at weeks 0, 4, and 8 was done using a two-way repeated-measures analysis of variance (two-way RM analysis of variance). Results: Patients initiated on escitalopram tended to show a higher rise in the IOP (left eye-[F = 3.27; P = 0.04]; right eye [F = 2.47; P = 0.08]). No difference was found in the iridocorneal angles in any of the four quadrants across both eyes. Conclusions: Escitalopram use had an association with an increase in IOP. While initiating patients on antidepressants, clinicians should be aware of this possibility, which can lead to ocular emergencies, and obtain a proper history of ocular morbidities.

Evaluation of post-operative dry eye in upper and lower eyelid reconstruction: A cross-sectional study.

Purpose: In cases of eyelid malignancies requiring full thickness excisional biopsy followed by reconstruction of the created defect, the Meibomian glands are lost. Post-operative varying degrees of dry eye disease (DED) are expected in such patients. The aim was to evaluate the objective and subjective statuses of DED in cases of full thickness eyelid reconstruction following excisional biopsy because of malignancies. Methods: This was a cross-sectional pilot study. Objective and subjective dry eye parameters are assessed in cases of full thickness eyelid reconstruction following excisional biopsy because of malignancies in 37 eyes at 6 months post-operative follow-up. Analysis of variance and Chi square test were used for statistical analysis. Results: When compared with fellow eye, all the parameters were found to be statistically significant (P < 0.0). Subjective assessment of dry eye by ocular surface disease index (OSDI) scoring did not corroborate with the objective data (p 0.00). Lower eyelid reconstruction showed a minimum number of dry eye cases (P > 0.05). Conclusion: Prevalence of post-operative dry eye is more with increasing percentage of full thickness upper eyelid reconstruction. Disparity was found between objective and subjective parameters of dry eye in patients requiring varying percentages of upper eyelid reconstruction because of malignancies.