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INTRODUCTION: The launch of injectable shorter regimens under Programmatic Management of Drug Resistant Tuberculosis (PMDT) guidelines 2017 under Revised National Tuberculosis Control Program (RNTCP) was a welcome step as it decreased the duration of treatment significantly in Drug Resistant Tuberculosis (DRTB) patients. The objective of the present study was to evaluate the treatment outcomes of patients started on injectable shorter regimens from March 2018 to May, 2019. METHODS: Retrospective study which scrutinized medical records of 85 patients started on injectable shorter regimen was conducted. Necessary information on possible patient and disease related predicting factors like age, gender, weight, HIV status, presence of diabetes mellitus (DM), anemia, gap between diagnosis and initiation of treatment, duration of intensive phase (IP) and time of sputum conversion was retrieved, and analyzed for possible association with treatment outcomes. RESULTS: 56.5% had successful treatment outcomes. Age, gender, BMI, diabetic/anemic status and gap between diagnosis and initiation of treatment had no statistically significant relationship with the final outcomes. Duration of IP, sputum conversion and time of outcome during the course of illness emerged as significant factors in successful outcomes. CONCLUSION: The injectable shorter regimens were suitable for a variety of population irrespective of demographic disparities. Patients need to be followed closely as microbiological parameters serve as early indicators of unsuccessful outcomes. These regimens can serve as an alternate choice in patients not tolerating the all oral shorter Bedaquiline containing shorter regimen. Similar such options with combinations of different drugs for individualizing treatment regimens is the need of the hour.

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In this paper, a novel one dimensional chaotic map $ K(x) = \frac{\mu x(1\, -x)}{1+ x} $, $ x\in [0, 1], \mu > 0 $ is proposed. Some dynamical properties including fixed points, attracting points, repelling points, stability and chaotic behavior of this map are analyzed. To prove the main result, various dynamical techniques like cobweb representation, bifurcation diagrams, maximal Lyapunov exponent, and time series analysis are adopted. Further, the entropy and probability distribution of this newly introduced map are computed which are compared with traditional one-dimensional chaotic logistic map. Moreover, with the help of bifurcation diagrams, we prove that the range of stability and chaos of this map is larger than that of existing one dimensional logistic map. Therefore, this map might be used to achieve better results in all the fields where logistic map has been used so far.

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Diffusion-driven instability and Turing pattern formation are a well-known mechanism by which the local interaction of species, combined with random spatial movement, can generate stable patterns of population densities in the absence of spatial heterogeneity of the underlying medium. Some examples of such patterns exist in ecological interactions between predator and prey, but the conditions required for these patterns are not easily satisfied in ecological systems. At the same time, most ecological systems exist in heterogeneous landscapes, and landscape heterogeneity can affect species interactions and individual movement behavior. In this work, we explore whether and how landscape heterogeneity might facilitate Turing pattern formation in predator-prey interactions. We formulate reaction-diffusion equations for two interacting species on an infinite patchy landscape, consisting of two types of periodically alternating patches. Population dynamics and movement behavior differ between patch types, and individuals may have a preference for one of the two habitat types. We apply homogenization theory to derive an appropriately averaged model, to which we apply stability analysis for Turing patterns. We then study three scenarios in detail and find mechanisms by which diffusion-driven instabilities may arise even if the local interaction and movement rates do not indicate it.

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A nitrogen plasma was incorporated into the cathode side of an electrolyzer to provide energetically activated N2 species to the electrocatalyst surface. At an applied bias of ∼3.5 V across the electrolyzer, plasma-assisted operation was observed to produce 47% more ammonia than the combination of plasma-without-bias and bias-without-plasma conditions.

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INTRODUCTION: Pulmonary tuberculosis has atypical radiological manifestations in patients with underlying immunocompromised disease like diabetes and human immunodeficient virus infection. Computed tomography has important role in such patients for early diagnosis of disease and management to minimize complication. AIM: To evaluate and compare the computed tomography chest features of pulmonary tuberculosis in between immunocompromised patients and immunocompetent patients. MATERIALS AND METHODS: This cross-sectional study was conducted in the hospital on newly diagnosed 60 pulmonary tuberculosis patients of which 30 patients had no underlying disease (Immunocompetent Group) and 30 patients had diabetes mellitus or were human immunodeficiency virus seropositive (Immunocompromised Group). CT scan of chest were evaluated for each patient. RESULTS: In immunocompetent patients, 36.7% had radiologically atypical presentation,90% had nodular opacities, 73.3% had consolidation, 23.3% had lymphadenopathy, 60% had cavitation and cavitatory lesion were single in 94.4% patients. Isolated upper lung field were involved in 60% patients. In immunocompromised patients 76.7% had radiologically atypical presentation, 66.7% had nodular opacities, 46.7% had consolidation, 63.3% had lymphadenopathy, 20% had cavitation and cavitatory lesions were multiple in 60% patients. Isolated lower lung field were involved in 23.3% patients. CONCLUSION: We concluded that immunocompromised patients have more atypical involvement of lung fields, higher prevalence of lymphadenopathy as compared to immunocompetent patients. Diabetic patients have multiple cavitatory lesions as compared to non-diabetic patients. HIV seropositive patients have more prevalence of lymphadenopathy as compared to HIV seronegative patients.

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Electrochemical conversion of CO2 into energy-dense liquids, such as formic acid, is desirable as a hydrogen carrier and a chemical feedstock. SnOx is one of the few catalysts that reduce CO2 into formic acid with high selectivity but at high overpotential and low current density. We show that an electrochemically reduced SnO2 porous nanowire catalyst (Sn-pNWs) with a high density of grain boundaries (GBs) exhibits an energy conversion efficiency of CO2 -into-HCOOH higher than analogous catalysts. HCOOH formation begins at lower overpotential (350 mV) and reaches a steady Faradaic efficiency of ca. 80 % at only -0.8 V vs. RHE. A comparison with commercial SnO2 nanoparticles confirms that the improved CO2 reduction performance of Sn-pNWs is due to the density of GBs within the porous structure, which introduce new catalytically active sites. Produced with a scalable plasma synthesis technology, the catalysts have potential for application in the CO2 conversion industry.

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La(C3H4) and La(C3H6) are observed from the reaction of laser-vaporized La atoms with propene by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. Two isomers of La(C3H4) are identified as methyl-lanthanacyclopropene [La(CHCCH3)] (Cs) and lanthanacyclobutene [La(CHCHCH2)] (C1); La(C3H6) is determined to be H-La(η3-allyl) (Cs), a C-H bond inserted species. All three metal-hydrocarbon radicals prefer a doublet ground state with a La 6s-based electron configuration. Ionization of the neutral doublet state of each of these radicals produces a singlet ion state by removing the La-based 6s electron. The threshold ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. The formation of the three radicals is investigated by density functional theory computations. The inserted species is formed by La inserting into an allylic C-H bond and lanthanacyclopropene by concerted vinylic H2 elimination, whereas lanthanacyclobutene involves both allylic and vinylic dehydrogenations. The inserted species is identified as an intermediate for the formation of lanthanacyclobutene.

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A Ce atom reaction with ethylene was carried out in a laser-vaporization metal cluster beam source. Ce(C2H2) formed by hydrogen elimination from ethylene was investigated by mass-analyzed threshold ionization (MATI) spectroscopy, isotopic substitutions, and relativistic quantum chemical computations. The theoretical calculations include a scalar relativistic correction, dynamic electron correlation, and spin-orbit coupling. The MATI spectrum exhibits two nearly identical band systems separated by 128 cm(-1). The separation is not affected by deuteration. The two-band systems are attributed to spin-orbit splitting and the vibrational bands to the symmetric metal-ligand stretching and in-plane carbon-hydrogen bending excitations. The spin-orbit splitting arises from interactions of a pair of nearly degenerate triplets and a pair of nearly degenerate singlets. The organolanthanide complex is a metallacyclopropene in C2v symmetry. The low-energy valence electron configurations of the neutral and ion species are Ce 4f(1)6s(1) and Ce 4f(1), respectively. The remaining two electrons that are associated with the isolated Ce atom or ion are spin paired in a molecular orbital that is a bonding combination between a 5d Ce orbital and a π* antibonding orbital of acetylene.

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La(C2H2) and La(C4H6) are observed from the reaction of laser-vaporized La atoms with ethylene molecules by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. La(C2H2) is identified as a metallacyclopropene and La(C4H6) as a metallacyclopentene. The three-membered ring is formed by concerted H2 elimination and the five-membered cycle by dehydrogenation and C-C bond coupling. Both metallacycles prefer a doublet ground state with a La 6s-based unpaired electron. Ionization of the neutral doublet state of either complex produces a singlet ion state by removing the La-based electron. The ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal-hydrocarbon cycles are lower than that of the neutral La atom. Deuteration has a small effect on the ionization energies of the two cyclic radicals but distinctive effects on their vibrational frequencies.

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Degradation of metal-organic halide perovskites when exposed to ambient conditions is a crucial issue that needs to be addressed for commercial viability of perovskite solar cells (PSCs). Here, a concept of encapsulating CH3NH3PbI3 perovskite crystals with a multi-functional graphene-polyaniline (PANI) composite coating to protect the perovskite against degradation from moisture, oxygen and UV light is presented. Hole-conducting polymers containing 2D layered sheet materials are presented here as multi-functional materials with oxygen and moisture impermeability. Specific studies involving PANI and graphene composites as coatings for perovskite crystals exhibited resistance to moisture and oxygen under continued exposure to UV and visible light. Most importantly, no perovskite degradation was observed even after 96 h of exposure of the PSCs to extremely high humidity (99% relative humidity). Our observations and results on perovskite protection with graphene/conducting polymer composites open up opportunities for glove-box-free and atmospheric processing of PSCs.

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Perovskite solar cells utilizing a two-step deposited CH3NH3PbI3 thin film were rapidly sintered using an intense pulsed light source. For the first time, a heat treatment has shown the capability of sintering methylammonium lead iodide perovskite and creating large crystal sizes approaching 1 µm without sacrificing surface coverage. Solar cells with an average efficiency of 11.5% and a champion device of 12.3% are reported. The methylammonium lead iodide perovskite was subjected to 2000 J of energy in a 2 ms pulse of light generated by a xenon lamp, resulting in temperatures significantly exceeding the degradation temperature of 150 °C. The process opens up new opportunities in the manufacturability of perovskite solar cells by eliminating the rate-limiting annealing step, and makes it possible to envision a continuous roll-to-roll process similar to the printing press used in the newspaper industry.

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η(2)-Propadienylidenelanthanum [La(η(2)-CCCH2)] and deprotiolanthanacyclobutadiene [La(HCCCH)] of La(C3H2) are identified from the reaction mixture of neutral La atom activation of propyne in the gas phase. The two isomers are characterized with mass-analyzed threshold ionization spectroscopy combined with electronic structure calculations and spectral simulations. La(η(2)-CCCH2) and La(HCCCH) are formed by concerted 1,3- and 3,3-dehydrogenation, respectively. Both isomers prefer a doublet ground state with a La 6s-based unpaired electron, and La(η(2)-CCCH2) is slightly more stable than La(HCCCH). Ionization of the neutral doublet state of either isomer produces a singlet ion state by removing the La-based electron. The geometry change upon ionization results in the excitation of a symmetric metal-hydrocarbon stretching mode in the ionic state, whereas thermal excitation leads to the observation of the same stretching mode in the neutral state. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal-hydrocarbon radicals are lower than that of the neutral La atom. Deuteration has a very small effect on the ionization energies of the two isomers and the metal-hydrocarbon stretching mode of La(η(2)-CCCH2), but it reduces considerably the metal-ligand stretching frequencies of La(HCCCH).

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Group 6 metal-bis(mesitylene) sandwich complexes are produced by interactions between the laser-vaporized metal atoms and mesitylene vapor in a pulsed molecular beam source, identified by photoionization time-of-flight mass spectrometry, and studied by pulsed-field ionization zero-electron kinetic energy spectroscopy and density functional theory calculations. Although transition metal-bis(arene) sandwich complexes may adopt eclipsed and staggered conformations, the group 6 metal-bis(mesitylene) complexes are determined to be in the eclipsed form. In this form, rotational conformers with methyl group dihedral angles of 0 and 60° are identified for the Cr complex, whereas the 0° rotamer is observed for the Mo and W species. The 0° rotamer is in a C(2v) symmetry with the neutral ground state of (1)A1 and the singly positive charged ion state of (2)A1. The 60° rotamer is in a C(i) symmetry with the neutral ground state of (1)A(g) and the ion state of (2)A(g). Partial conversion of the 60 to 0° rotamer is observed from He to He/Ar supersonic expansion for Cr-bis(mesitylene). The unsuccessful observation of the 60° rotamer for the Mo and W complexes is the result of its complete conversion to the 0° rotamer in both He and He/Ar expansions. The adiabatic ionization energies of the 0° rotamers of the three complexes are in the order of Cr-bis(mesitylene) < W-bis(mesitylene) < Mo-bis(mesitylene), which is different from that of the metal atoms. These metal-bis(mesitylene) complexes have lower ionization energies than the corresponding metal-bis(benzene) and -bis(toluene) species.

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Group 3 metal-aniline complexes, M(aniline) (M = Sc, Y, and La), are produced in a pulsed laser-vaporization molecular beam source, identified by photoionization time-of-flight mass spectrometry, and investigated by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and quantum chemical calculations. Adiabatic ionization energies and several low-frequency vibrational modes are measured for the first time from the ZEKE spectra. Metal binding sites and electronic states are determined by combining the ZEKE measurements with the theoretical calculations. The ionization energies of the complexes decrease down the metal group. An out-of-plane ring deformation mode coupled with an asymmetric metal-carbon stretch is considerably anharmonic. Although aniline has various possible sites for metal coordination, the preferred site is the phenyl ring. The metal binding with the phenyl ring yields syn and anti conformers with the metal atom and amino hydrogens on the same and opposite sides of the ring, respectively. The anti conformer is determined to be the spectral carrier. The ground electronic state of the anti conformer of each neutral complex is a doublet with a metal-based electron configuration of nd(2)(n + 1)s(1), and the ground electronic state of each ion is a singlet with a metal-based electron configuration of nd(2). The formation of the neutral complexes requires the nd(2)(n + 1)s(1) ← nd(1)(n + 1)s(2) electron excitation in the metal atoms.

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Cerium, praseodymium, and neodymium complexes of 1,3,5,7-cyclooctatetraene (COT) complexes were produced in a laser-vaporization metal cluster source and studied by pulsed-field ionization zero electron kinetic energy spectroscopy and quantum chemical calculations. The computations included the second-order Møller-Plesset perturbation theory, the coupled cluster method with single, double, and perturbative triple excitations, and the state-average complete active space self-consistent field method. The spectrum of each complex exhibits multiple band systems and is assigned to ionization of several low-energy electronic states of the neutral complex. This observation is different from previous studies of M(COT) (M = Sc, Y, La, and Gd), for which a single band system was observed. The presence of the multiple low-energy electronic states is caused by the splitting of the partially filled lanthanide 4f orbitals in the ligand field, and the number of the low-energy states increases rapidly with increasing number of the metal 4f electrons. On the other hand, the 4f electrons have a small effect on the geometries and vibrational frequencies of these lanthanide complexes.

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Monobenzene complexes of yttrium (Y), lanthanum (La), and lutetium (Lu), M(C(6)H(6)) (M = Y, La, and Lu), were prepared in a laser-vaporization supersonic molecular beam source and studied by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and ab initio calculations. The calculations included the second-order perturbation, the coupled cluster with single, double, and perturbative triple excitation, and the complete active space self-consistent field methods. Adiabatic ionization energies and metal-benzene stretching frequencies of these complexes were measured for the first time from the ZEKE spectra. Electronic states of the neutral and ion complexes and benzene ring deformation were determined by combining the spectroscopic measurements with the theoretical calculations. The ionization energies of M(C(6)H(6)) are 5.0908 (6), 4.5651 (6), and 5.5106 (6) eV, and the metal-ligand stretching frequencies of [M(C(6)H(6))](+) are 328, 295, and 270 cm(-1) for M = Y, La, and Lu, respectively. The ground states of M(C(6)H(6)) and [M(C(6)H(6))](+) are (2)A(1) and (1)A(1), respectively, and their molecular structures are in C(2v) point group with a bent benzene ring. The deformation of the benzene ring upon metal coordination is caused by the pseudo Jahn-Teller interaction of (1(2)E(2)+1(2)A(1)+2(2)E(2)) e(2) at C(6v) symmetry. In addition, the study shows that spectroscopic behaviors of Y(C(6)H(6)) and La(C(6)H(6)) are similar to each other, but different from that of Lu(C(6)H(6)).

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Gadolinium (Gd) complexes of benzene (C(6)H(6)) and (1,3,5,7-cyclooctatetraene) (C(8)H(8)) were produced in a laser-vaporization supersonic molecular beam source and studied by single-photon pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy. Adiabatic ionization energies and metal-ligand stretching frequencies were measured for the first time from the ZEKE spectra. Metal-ligand bonding and electronic states of the neutral and cationic complexes were analyzed by combining the spectroscopic measurements with ab initio calculations. The ground states of Gd(C(6)H(6)) and [Gd(C(6)H(6))](+) were determined as (11)A(2) and (10)A(2), respectively, with C(6v) molecular symmetry. The ground states of Gd(C(8)H(8)) and [Gd(C(8)H(8))](+) were identified as (9)A(2) and (8)A(2), respectively, with C(8v) molecular symmetry. Although the metal-ligand bonding in Gd(C(6)H(6)) is dominated by the covalent interaction, the bonding in Gd(C(8)H(8)) is largely electrostatic. The bonding in the benzene complex is much weaker than that in the cyclooctatetraene species. The strong bonding in Gd(C(8)H(8)) arises from two-electron transfer from Gd to C(8)H(8), which creates a strong charge-charge interaction and converts the tub-shaped ligand into a planar form. In both systems, Gd 4f orbitals are localized and play little role in the bonding, but they contribute to the high electron spin multiplicities.

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Group 6 metal (Cr, Mo, and W)-bis(toluene) sandwich complexes are synthesized in a laser-vaporization molecular beam source. Conformational isomers and isomerization of these complexes are studied by variable-temperature pulsed-field-ionization zero-electron-kinetic-energy spectroscopy and density functional theory. For Cr-bis(toluene), four rotational conformers are identified with methyl-group dihedral angles of 0, 60, 120, and 180°. The ground electronic states of these conformers are (1)A(1) (C(2v), 0°), (1)A (C(2), 60 and 120°), and (1)A(g) (C(2h), 180°) in the neutral form and (2)A(1) (C(2v), 0°), (2)A (C(2), 60 and 120°), and (2)A(g) (C(2h), 180°) in the singly charged cationic form. For Mo- and W-bis(toluene), the four rotamers are resolved into three (0, 60/120, and 180°) and two (0 and 60/120/180°) groups, respectively. For all three metal sandwiches, the most stable conformer is in the complete eclipsed configuration (0°) and has the highest ionization energy. The conversion from 60/120/180° to 0° rotamer is observed from helium to argon supersonic expansions and is more efficient for the heavier Mo and W species.

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Scandium (Sc) complexes of p-xylene, mesitylene, and hexamethylbenzene were produced in a laser-vaporization molecular beam source and studied with pulsed-field-ionization zero-electron-kinetic-energy spectroscopy, and density functional theory. In addition, infrared-ultraviolet resonant two-photon ionization spectra were recorded for Sc(hexamethylbenzene) in the C-H stretching region. Adiabatic ionization energies and several vibrational frequencies of these complexes were obtained from the spectroscopic measurements, and electronic transitions were determined by combining the spectra with the theoretical data. The ionization energies of the three complexes decrease with increasing number of the methyl groups, whereas the metal-ligand stretching frequencies of the p-xylene and mesitylene complexes are essentially the same and slightly smaller than that of the hexamethylbenzene species. Unlike benzene, the arene ring of the methylbenzene molecules is bent and the pi-electrons are localized in a 1,4-diene fashion upon Sc coordination. The distortion of the aromatic ring is due to differential metal binding with the ring carbon atoms in the low-spin ground electronic state.