ABSTRACT
A hallmark of typical structural transformations is an increase in symmetry upon heating due to entropic favourability. However, local symmetry breaking upon warming is recently evidenced in rare crystalline phases. Termed as emphanisis, the phenomenon implores exploration of fascinating thermodynamic nuances that drive unusual structural evolutions. Here, synchrotron X-ray total scattering measurements are presented on a Ruddlesden-Popper mixed halide perovskite, Cs2PbI2Cl2, which reveal signatures of emphanisis. The genesis of symmetry lowering upon heating is traced to a lone pair-driven cooperative local structural distortion composed of thermally actuated Pb off-centring and static Cl displacement. Mapping the thermal evolution of low-lying phonon modes with inelastic neutron scattering uncovers instances of mode hardening with picosecond lifetime and an intriguing soft mode at the X-point of the Brillouin zone-features conducive to ultralow thermal transport. Together, these observations highlight the fundamental and functional implications of chemical design in engendering unconventional phenomena in crystalline materials and associated properties.
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Traditional catalyst development relies on multistep synthesis and isolation of ligand and precatalyst. Designing a catalytic system that can be assembled in situ from easily accessible starting materials can decrease the reaction complexity and enhance the synthetic utility. Herein, we report an inexpensive and commercially available CoBr2·H2O/terpyridine-catalyzed effective and straightforward transfer hydrogenation (TH) protocol for N-heteroarenes, utilizing NH3·BH3 (AB) under ambient conditions. Synthesis of diverse substrates and bioactive molecules demonstrated a practical applicability. Control experiments and DFT studies elucidate the mechanism.
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Three new hetero-metallic CuII-LnIII complexes [(CuL)Gd(NO3)3(CH3OH)]n (1), [(CuL)Tb(NO3)3(H2O)]·[CuL] (2) and [(CuL)Dy(NO3)3(H2O)]·[CuL] (3) have been synthesized using a mono-nuclear Cu(II) complex, [CuL], of an unsymmetrically di-condensed N2O3 donor Schiff base ligand, N-(3-methoxysalicylidene)-N-(salicylidene)-1,2-ethylenediamine (H2L). Single crystal X-ray crystallography revealed that complex 1 is a nitrate bridged 1D chain of dinuclear Cu(II)-Gd(III) units whereas in 2 and 3, the dinuclear Cu(II)-Ln(III) units are co-crystallized with a [CuL] unit. The Ln(III) centers are nine coordinated with the geometry of a spherical capped square antiprism for Gd and spherical tricapped trigonal prism for Tb and Dy. The geometry of the Cu(II) center is distorted octahedral for complex 1 and distorted square planar for complexes 2 and 3. Temperature-dependent molar magnetic susceptibility measurements in 1-3 revealed the presence of overall ferromagnetic coupling between the Cu(II) and Ln(III) centers. Notably, field induced single-molecule magnet behavior was witnessed in the Tb(III) derivative (2). The ab initio calculations indicated that upon application of an external magnetic field, the tunneling in the ground state of complex 2 gets reduced and thereby field-induced SMM behaviour is observed. Besides, in the case of complex 1, BS-DFT calculations were carried out to gain further insights into the magnetic exchange coupling interactions between the Cu(II) and Gd(III) centers.
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Oxazine-6-one and 4-pyrimidinol are two important frameworks in pharmaceutical production. Herein, we disclosed a simple, efficient, inexpensive organic base-promoted and additive-stimulated protocol for the syntheses of variably functionalized oxazine-6-ones and 4-pyrimidinols employing acetonitrile solvent under conventional heating conditions using an oil bath through C-N and C-O coupled domino steps. This simple practicable productive protocol utilizes easily producible cheap precursors, namely, benzimidates or benzamidines, with differently substituted dicyano-olefins, and it comprises step economy, robustness, and moisture insensitive conditions affording high yield that avoids the use of transition-metal catalysts, multistep with multicomponent strategy, and harsh reaction conditions involving hazardous chemicals. This method is scalable into gram-scale production with good yield.
ABSTRACT
N-heterocyclic carbene catalysis reaction protocol is disclosed for the synthesis of phthalidyl sulfonohydrazones. A broad range of N-tosyl hydrazones react effectively with phthalaldehyde derivatives under open-air conditions, enabling the formation of a new C-N bond via an oxidative path. The reaction proceeds under mild reaction conditions with broad substrate scopes, wide functional group tolerance, and good to excellent yields. The mechanistic pathway is studied successfully using control experiments, competitive reactions, ESI-MS spectral analyses of the reaction mixture, and computational study by density functional theory. The potential use of one of the phthalidyl sulfonohydrazone derivatives as the inhibitor of ß-ketoacyl acyl carrier protein synthase I of Escherichia coli is investigated using molecular docking.
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Adherent cells ensure membrane homeostasis during de-adhesion by various mechanisms, including endocytosis. Although mechano-chemical feedbacks involved in this process have been studied, the step-by-step build-up and resolution of the mechanical changes by endocytosis are poorly understood. To investigate this, we studied the de-adhesion of HeLa cells using a combination of interference reflection microscopy, optical trapping and fluorescence experiments. We found that de-adhesion enhanced membrane height fluctuations of the basal membrane in the presence of an intact cortex. A reduction in the tether force was also noted at the apical side. However, membrane fluctuations reveal phases of an initial drop in effective tension followed by saturation. The area fractions of early (Rab5-labelled) and recycling (Rab4-labelled) endosomes, as well as transferrin-labelled pits close to the basal plasma membrane, also transiently increased. On blocking dynamin-dependent scission of endocytic pits, the regulation of fluctuations was not blocked, but knocking down AP2-dependent pit formation stopped the tension recovery. Interestingly, the regulation could not be suppressed by ATP or cholesterol depletion individually but was arrested by depleting both. The data strongly supports Clathrin and AP2-dependent pit-formation to be central to the reduction in fluctuations confirmed by super-resolution microscopy. Furthermore, we propose that cholesterol-dependent pits spontaneously regulate tension under ATP-depleted conditions.
Subject(s)
Clathrin , Coated Pits, Cell-Membrane , Humans , Clathrin/metabolism , Coated Pits, Cell-Membrane/metabolism , HeLa Cells , Endocytosis/physiology , Cholesterol/metabolism , Adenosine Triphosphate/metabolism , Cell Membrane/metabolismABSTRACT
Achieving glass-like ultra-low thermal conductivity in crystalline solids with high electrical conductivity, a crucial requirement for high-performance thermoelectrics , continues to be a formidable challenge. A careful balance between electrical and thermal transport is essential for optimizing the thermoelectric performance. Despite this inherent trade-off, the experimental realization of an ideal thermoelectric material with a phonon-glass electron-crystal (PGEC) nature has rarely been achieved. Here, PGEC-like AgSbTe2 is demonstrated by tuning the atomic disorder upon Yb doping, which results in an outstanding thermoelectric performance with figure of merit, zT ≈ 2.4 at 573 K. Yb-doping-induced enhanced atomic ordering decreases the overlap between the hole and phonon mean free paths and consequently leads to a PGEC-like transport behavior in AgSbTe2 . A twofold increase in electrical mobility is observed while keeping the position of the Fermi level (EF ) nearly unchanged and corroborates the enhanced crystalline nature of the AgSbTe2 lattice upon Yb doping for electrical transport. The cation-ordered domains, lead to the formation of nanoscale superstructures (≈2 to 4 nm) that strongly scatter heat-carrying phonons, resulting in a temperature-independent glass-like thermal conductivity. The strategy paves the way for realizing high thermoelectric performance in various disordered crystals by making them amorphous to phonons while favoring crystal-like electrical transport.
ABSTRACT
Defect engineering, achieved by precise tuning of the atomic disorder within crystalline solids, forms a cornerstone of structural chemistry. This nuanced approach holds the potential to significantly augment thermoelectric performance by synergistically manipulating the interplay between the charge carrier and lattice dynamics. Here, the current study presents a distinctive investigation wherein the introduction of Hg doping into AgSbTe2 serves to partially curtail structural disorder. This strategic maneuver mitigates potential fluctuations originating from pronounced charge and size disparities between Ag+ and Sb3+, positioned in octahedral sites within the rock salt structure. Hg doping significantly improves the phase stability of AgSbTe2 by restricting the congenital emergence of the Ag2Te minor secondary phase and promotes partial atomic ordering in the cation sublattice. Reduction in atomic disorder coalesced with a complementary modification of electronic structure by Hg doping results in increased carrier mobility. The formation of nanoscale superstructure with sizes (2-5 nm) of the order of phonon mean free path in AgSbTe2 is further promoted by reduced partial disorder, causes enhanced scattering of heat-carrying phonons, and results in a glass-like ultralow lattice thermal conductivity (â¼0.32 W m-1 K-1 at 297 K). Cumulatively, the multifaceted influence of Hg doping, in conjunction with the consequential reduction in disorder, allows achieving a high thermoelectric figure-of-merit, zT, of â¼2.4 at â¼570 K. This result defies conventional paradigms that prioritize increased disorder for optimizing zT.
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Doping is usually the first step to tailor thermoelectrics. It enables precise control of the charge-carrier concentration and concomitant transport properties. Doping should also turn GeSe, which features an intrinsically a low carrier concentration, into a competitive thermoelectric. Yet, elemental doping fails to improve the carrier concentration. In contrast, alloying with Ag-V-VI2 compounds causes a remarkable enhancement of thermoelectric performance. This advance is closely related to a transition in the bonding mechanism, as evidenced by sudden changes in the optical dielectric constant ε∞ , the Born effective charge, the maximum of the optical absorption ε2 (ω), and the bond-breaking behavior. These property changes are indicative of the formation of metavalent bonding (MVB), leading to an octahedral-like atomic arrangement. MVB is accompanied by a thermoelectric-favorable band structure featuring anisotropic bands with small effective masses and a large degeneracy. A quantum-mechanical map, which distinguishes different types of chemical bonding, reveals that orthorhombic GeSe employs covalent bonding, while rhombohedral and cubic GeSe utilize MVB. The transition from covalent to MVB goes along with a pronounced improvement in thermoelectric performance. The failure or success of different dopants can be explained by this concept, which redefines doping rules and provides a "treasure map" to tailor p-bonded chalcogenides.
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This study evaluates the volumetric modulated arc therapy (VMAT) dosimetric comparison between Halcyon ring gantry and TrueBeam c-arm linear accelerators for craniospinal irradiation (CSI) of the neuro-axis. 25 patients, who received treatment for medulloblastoma and primitive neuro-ectodermal tumors between 2018 and 2021, were planned for VMAT in True Beam (TB), and Halcyon (HAL) linear accelerators using 6 MV unflattened (FFF) photon beams (HALFFF and TBFFF). Dose-volume statistics for the target and organs at risk (OARs) and the total number of monitoring units (MUs) in the treatment plans were compared which included dose received by 95% PTV volume (V95%), volume receiving ≥ 107% dose, homogeneity index (HI), conformity index (PI), MU and dose spillage (D10%, D30%, D50%, D70%, D90%). In all 26 OARs were considered of which five were serial and the remaining were parallel structures. For the former, the dose received by 0.2 cm3, volume = D0.2 cm3) were evaluated and for the latter mean dose were evaluated. Both arms were statistically compared with paired sample t-test with a significant value of ≤ 0.05. 11 patients received treatment with the Halcyon and the rest 14 in the TrueBeam C-arm linear accelerator. Patients in the low- and intermediate-risk category (n = 13) received 23.4 Gy in 13 fractions. The remaining patients were in the high-risk category and received 35 Gy in 21 fractions or 36 Gy in 20 fractions. For HALFFF and TBFFF, PTVV95% were 97.5 ± 0.8% and 97.4 ± 0.9% respectively (p = 0.371) while the V107% were 0.6 ± 0.4% and 0.5 ± 0.5 respectively (p = 0.504). However, the number of monitoring units showed statistical significance (p < 0.001) with values of 1331.9 ± 243.4 MU and 1089 ± 206.7 MU respectively for the HAL and TB plans. The differences in spillage dose were also statistically significant, favouring HAL plans at D30% (p = 0.002), D50% (p < 0.001), D70% (p = 0.039), and D90% (p = 0.01) level except for D10% (p = 0.090). Conformity index also showed statistical significance with PI_HAL = 0.9 ± 0.02 and PI_TB = 0.89 ± 0.03 (p = 0.029). For 10 of the 21 parallel structures, the mean dose differences were statistically significant in favouring of HAL plans. Halcyon based VMAT CSI plans are dosimetrically superior in terms of organ dose, especially for the large organs, and offer lower spillage doses than the TrueBeam plans. Plans generated by both linear accelerators are suitable for the patients' treatments.
Subject(s)
Cerebellar Neoplasms , Craniospinal Irradiation , Radiotherapy, Intensity-Modulated , Animals , Humans , Radiometry , BirdsABSTRACT
The occurrence of overweight and obesity has increased in recent years in India. In this study, we investigate the prevalence and associated risk factors of overweight/obesity among children aged 0-59 months in India. Using data from the 2015-2016 National Family Health Survey-4 (NFHS-4), the research sample included 176,255 children aged 0 to 59 months. Bivariate and multivariate techniques were used to analyze children's risk factors for overweight/obesity. We identified that the prevalence of overweight/obesity among children aged 0-59 was 2.6% in India. The study findings reveal that factors such as child sex, age, birth weight, birth rank, maternal education, number of children, age at marriage, mother's BMI, media exposure, social group, and dietary diversity score were most significantly correlated with childhood overweight and obesity in India. Furthermore, we found that male children (ARR: 1.08) aged between 0 and 11 months (ARR: 3.77) with low birth rank (ARR: 1.24), obese (ARR: 1.81) children whose mothers married after the age of 18 (ARR: 1.15), children who belong to a scheduled tribe family (ARR: 1.46), and children who consumed 7-9 food items (ARR: 1.22) were at highest risk of being overweight and obese. However, breastfeeding (ARR: 0.85) and Muslim families (ARR: 0.87) appeared to be protective factors with respect to childhood overweight and obesity in India. Pertinent public health programs, clinical follow-up, and awareness about sedentary lifestyles can help to reduce overweight/obesity risks in children.
Subject(s)
Overweight , Pediatric Obesity , Body Mass Index , Child , Cross-Sectional Studies , Female , Health Surveys , Humans , India/epidemiology , Infant , Infant, Newborn , Male , Overweight/epidemiology , Pediatric Obesity/epidemiology , Prevalence , Risk FactorsABSTRACT
As the periodic atomic arrangement of a crystal is made to a disorder or glassy-amorphous system by destroying the long-range order, lattice thermal conductivity, κL, decreases, and its fundamental characteristics changes. The realization of ultralow and unusual glass-like κL in a crystalline material is challenging but crucial to many applications like thermoelectrics and thermal barrier coatings. Herein, we demonstrate an ultralow (~0.20 W/m·K at room temperature) and glass-like temperature dependence (2-400 K) of κL in a single crystal of layered halide perovskite, Cs3Bi2I6Cl3. Acoustic phonons with low cut-off frequency (20 cm-1) are responsible for the low sound velocity in Cs3Bi2I6Cl3 and make the structure elastically soft. While a strong anharmonicity originates from the low energy and localized rattling-like vibration of Cs atoms, synchrotron X-ray pair-distribution function evidence a local structural distortion in the Bi-halide octahedra and Cl vacancy. The hierarchical chemical bonding and soft vibrations from selective sublattice leading to low κL is intriguing from lattice dynamical perspective as well as have potential applications.
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AIM: This study aimsâ to report preclinical validation, and the first clinical treatment of total bone marrow irradiation (TMI) and total bone marrow and lymph nodal irradiation (TMLI) using Volumetric modulated arc therapy in Halcyon-E ring gantry linear accelerator. Preclinical validation includes simulation, planning, patient-specific QA, and dry run. MATERIAL AND METHOD: Four patients, two female and two male, with body weights of 116 kg, 52 kg, 64 kg, and 62 kg; with two with chronic myeloid leukemia, one each with acute lymphoblastic leukemia and acute myeloid leukemia (AML) were simulated and planned for TMI/TMLI. Patients were immobilized with a full-body vacuum bag. Head first supine (HFS) and Feet first supine (FFS) CT scans were acquired from head to knee and knee to toe. Planning target volume (PTV) was created with a uniform margin of 6 mm over the total bone marrow/bone marrow + lymph nodes. HFS and FFS PTVs were optimized independently using 6MV unflatten energy for 12 Gy in 6 fractions. Plans were merged to create the resultant dose distribution using a junction bias dose matching technique. The total number of isocenters was ≤ 10 per CT set, and two to four full arcs were used for each isocenter. A junction dose gradient technique was used for dose feathering between arcs between adjacent isocenters. RESULT: Only one female patient diagnosed as AML received the TMLI treatment, while the other three patients dropped out due to clinical complications and comorbidities that developed in the time between simulation and treatment. The result presented has been averaged over all four patients. For PTV, 95% dose was normalised to 95% volume, PTV_V107% receiving 3.3 ± 3.1%. Total lung mean and V12Gy were 1048.6 ± 107.1 cGy and 19.5 ± 12.1%. Maximum lens doses were 489.5 ± 35.5 cGy (left: L) and 497 ± 69.2 cGy (right: R). The mean cardiac and bilateral kidney doses were 921.75 ± 89.2 cGy, 917.9 ± 63.2 cGy (L), and 805.9 ± 9.7 cGy (R). Average Monitor Unit was 7738.25 ± 1056.6. The median number of isocenters was 17(HFS+FFS), average MU/Dose (cGy) ratio per isocenter was 2.28 ± 0.3. CONCLUSION: Halcyon-E ring gantry linear accelerator capable of planning and delivering TMI/TMLI.ââ.
Subject(s)
Leukemia, Myeloid, Acute , Radiotherapy, Intensity-Modulated , Female , Humans , Male , Bone Marrow/radiation effects , Particle Accelerators , Radiotherapy Dosage , Radiotherapy Planning, Computer-Assisted/methods , Radiotherapy, Intensity-Modulated/methodsABSTRACT
Efficient manipulation of thermal conductivity and fundamental understanding of the microscopic mechanisms of phonon scattering in crystalline solids are crucial to achieve high thermoelectric performance. Thermoelectric energy conversion directly and reversibly converts between heat and electricity and is a promising renewable technology to generate electricity by recovering waste heat and improve solid-state refrigeration. However, a unique challenge in thermal transport needs to be addressed to achieve high thermoelectric performance: the requirement of crystalline materials with ultralow lattice thermal conductivity (κL). A plethora of strategies have been developed to lower κL in crystalline solids by means of nanostructural modifications, introduction of intrinsic or extrinsic phonon scattering centers with tailored shape and dimension, and manipulation of defects and disorder. Recently, intrinsic local lattice distortion and lattice anharmonicity originating from various mechanisms such as rattling, bonding heterogeneity, and ferroelectric instability have found popularity. In this Perspective, we outline the role of manipulation of chemical bonding and structural chemistry on thermal transport in various high-performance thermoelectric materials. We first briefly outline the fundamental aspects of κL and discuss the current status of the popular phonon scattering mechanisms in brief. Then we discuss emerging new ideas with examples of crystal structure and lattice dynamics in exemplary materials. Finally, we present an outlook for focus areas of experimental and theoretical challenges, possible new directions, and integrations of novel techniques to achieve low κL in order to realize high-performance thermoelectric materials.
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Background: The Covid-19 pandemic has a significant impact on education and mental health outcomes. This study attempts to analyze the factors associated with academic satisfaction level, psychological stress/anxiety, and future academic risk among Indian students of higher education in the wake of the Covid-19 pandemic. Methods: An online survey was conducted through a structured questionnaire among students of higher education. Multivariate ordered logistic regression models were performed to find out the predictors of perceived academic satisfaction level, psychological stress, and academic risk among the participants. Results: Among the 630 participants, the majority of the students (73%) had low to moderate levels of academic satisfaction. Over two-thirds of participants (68%) had a high level of stress and nearly two-fifths (38%) of the participants felt very high risk in their academic career. The multivariate logistic regression models show that the likelihood of psychological stress and academic risk was significantly higher among students aged above 25 years, researchers, and those who belong to broken families. Besides, the higher probability of satisfaction level is associated with female students, undergraduates, belonging to economically well-off families, and rural residents. Conclusion: Our study suggests that the Covid-19 pandemic leads to a range of psychological health problems. Therefore, increase students' satisfaction with online classes and it is essential to preserve the mental health of individuals and to develop psychological interventions that can improve the mental health of students during the Covid-19 pandemic.
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A mononuclear uranyl complex, [UO2L] (1), has been synthesized with the ligand N,N'-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane (H2L). The complex showed a reversible U(VI)/U(V) redox couple in cyclic voltammetric measurements. The reduction potential of this couple showed a positive shift upon the addition of redox-inactive alkali- and alkaline-earth Lewis acidic metal ions (Li+, Na+, K+, Ca2+, Sr2+, and Ba2+) to an acetonitrile solution of complex 1. The positive shift of the reduction potential has been explained on the basis of the Lewis acidity and internal electric-field effect of the respective metal ions. The bimetallic complexes [UO2LLi(NO3)] (2), [UO2LNa(BF4)]2 (3), [UO2LK(PF6)]2 (4), [(UO2L)2Ca]·(ClO4)2·CH3CN (5), [(UO2L)2Sr(H2O)2]·(ClO4)2·CH3CN (6), and [(UO2L)2Ba(ClO4)]·(ClO4) (7) have also been isolated in the solid state by reacting complex 1 with the corresponding metal ions and characterized by single-crystal X-ray diffraction. Density functional theory calculations of the optimized [UO2LM]n+ complexes have been used to rationalize the experimental reduction and electric-field potentials imposed by the non-redox-active cations.
ABSTRACT
Low dietary diversity significantly interplays with children's growth failure. However, evidence of its crucial role in children's health remains inconclusive in developing countries such as India. This study attempts to find the association between dietary diversity and growth outcomes among children aged between 6 and 23 months in India using the fourth round of the National Family Health Survey (NFHS), 2015−2016. A total of 67,278 mother-child pairs of children between the ages of 6−23 months and mothers aged 15−49 years were included in this study. Pearson's chi-square significance test and multivariable logistic regression were used to determine the association between dietary diversity and child growth outcomes (stunted, wasted, and underweight). The study found that the prevalence of stunting and severe stunting among children aged between 6 and 23 months were 35.9% and 16.2%; 23.8% and 8.5% represented wasting, and severe wasting; and more than 32%, 10% were underweight and severely underweight respectively. This present study found that having an inadequate minimum dietary diversity (<4 food groups) significantly increases the risk of being stunted (adjusted odds ratio (AOR) = 1.29; 95% confidence interval (CI); 1.21−1.38), wasted (AOR = 1.29; 95% CI; 1.21−1.38), and underweight (AOR = 1.47; 95% CI; 1.39−1.56). Further, it was noted that children who did not intake dairy products, eggs, and other fruits and vegetables were more likely to be stunted, wasted, and underweight and more likely to be severely stunted, wasted, and underweight. Therefore, additional nutrition-specific interventions are urgently needed to strengthen and enhance existing feeding interventions aimed at improving infant and young child feeding (IYCF) practices, including complementary feeding practices among children aged between 6 and 23 months in India. The Government should focus such interventions more on states or regions where the prevalence of adequate minimum dietary diversity (MDD) and malnutrition is high.
Subject(s)
Malnutrition , Nutritional Status , Infant , Female , Humans , Child, Preschool , Thinness/epidemiology , Malnutrition/epidemiology , Growth Disorders/epidemiology , Cachexia , Eggs , India/epidemiology , Health SurveysABSTRACT
SnSe has emerged as one of the most promising materials for thermoelectric energy conversion due to its extraordinary performance in its single-crystal form and its low-cost constituent elements. However, to achieve an economic impact, the polycrystalline counterpart needs to replicate the performance of the single crystal. Herein, we optimize the thermoelectric performance of polycrystalline SnSe produced by consolidating solution-processed and surface-engineered SnSe particles. In particular, the SnSe particles are coated with CdSe molecular complexes that crystallize during the sintering process, forming CdSe nanoparticles. The presence of CdSe nanoparticles inhibits SnSe grain growth during the consolidation step due to Zener pinning, yielding a material with a high density of grain boundaries. Moreover, the resulting SnSe-CdSe nanocomposites present a large number of defects at different length scales, which significantly reduce the thermal conductivity. The produced SnSe-CdSe nanocomposites exhibit thermoelectric figures of merit up to 2.2 at 786 K, which is among the highest reported for solution-processed SnSe.
ABSTRACT
A new Ni(ii) complex [NiL] (complex 1) of an asymmetrically di-condensed N2O3 donor Schiff base ligand, N-salicylidene-N'-3-methoxysalicylidene-1,3-propanediamine (H2L), has been synthesized and utilized for the synthesis of three heterometallic complexes, [(NiL)2Mn(NCS)2(CH3OH)2]·CH3OH (2) [(NiL)2Mn(N(CN)2)2(CH3OH)2]·CH3OH (3) and [(NiL)2Mn2(N3)2(µ1,1-N3)2(CH3OH)2] (4). Single crystal X-ray diffraction analyses show that complexes 2 and 3 have linear trinuclear structures where two tridentate O3 donor (NiL) units are coordinated to the central octahedral Mn(ii) centre, whereas complex 4 has a centrosymmetric tetranuclear structure where two binuclear (NiL)Mn units are linked via two phenoxido and two µ1,1-N3 bridges. Among the heterometallic complexes (2-4), only 4 is active towards the catalytic oxidation of 3,5-di-tert-butylcatechol to the corresponding quinone. The turnover number for the aerobic oxidation of 3,5-DTBC is 935 h-1. ESI-mass spectra have been recorded to scrutinize the mechanistic pathway of this catalytic reaction. Variable temperature magnetic susceptibility measurements suggest that complexes 2-4 are antiferromagnetically coupled with coupling constants (J) of -4.84 and -5.23 cm-1 for complexes 2 and 3, respectively and J1 = -2.20 cm-1, J2 = 1.13 cm-1 and J3 = -1.12 cm-1 for complex 4. DFT calculations have been used to rationalize the magnetic super-exchange in complexes 2-4, by computing the theoretical coupling constants and analyzing the spin density plots.
Subject(s)
Coordination Complexes/metabolism , Manganese/metabolism , Nickel/metabolism , Nitrogen Oxides/metabolism , Oxidoreductases/metabolism , Biocatalysis , Coordination Complexes/chemical synthesis , Coordination Complexes/chemistry , Crystallography, X-Ray , Density Functional Theory , Ligands , Magnetic Phenomena , Manganese/chemistry , Models, Molecular , Molecular Structure , Nickel/chemistry , Nitrogen Oxides/chemistry , Oxidoreductases/chemistryABSTRACT
N-Heterocyclic carbene-catalyzed tandem Stetter-aldol reaction of phthalaldehyde and α,ß-unsaturated ketimines has been developed to afford functionalized naphthalen-1(2H)-one derivatives as the formal [4+2] annulation product. Interestingly, the reaction of aldimines led to the formation of isoquinoline derivatives instead of the expected indanone derivatives as a [4+1] annulation product.