In-situ biofabrication of bacterial nanocellulose (BNC)/graphene oxide (GO) nano-biocomposite and study of its cationic dyes adsorption properties.

In the present study, bacterial nanocellulose/graphene oxide nano-biocomposites (BNC-GO-NBCs) were fabricated by Komagataeibacter saccharivorans NUWB1 using an in-situ method involving three time-dependent approaches. Physicochemical studies showed that the chosen dried BNC-GO-NBC possessed a three-dimensional interconnected porous structure of BNC with GO layers embedded within the BNC fibrils. BNC-GO-NBC had a crystallinity index of 74.21 %, higher thermostability up to 380 °C and could withstand a tensile load of 84.72 MPa. N2 adsorption-desorption isotherm of the BNC-GO-NBC was found to be of type IV, suggesting a mesoporous type structure with a total pore volume and surface area of 6.232e-04 cc g-1 and 10.498 m2. BNC-GO-NBC exhibited remarkable adsorption capacity for two cationic dyes, Rhodamine B (RhB) and Acridine Orange (AO), and the adsorption data conformed well to the Langmuir isotherm (R2 = 0.99) and pseudo-second-order model. Thermodynamic studies indicated that the adsorption process was spontaneous and endothermic. Additionally, the BNC-GO-NBC displayed the potential for regeneration, with the ability to be recycled up to five times. Further, the antibacterial activity, cell cytotoxicity and oxidative stress assays of the BNC-GO-NBC revealed its non-cytotoxic nature. The findings of the present investigation evidently suggest the potentiality of BNC-GO-NBC in the application of dye adsorption and other environmental applications.

A Radiative Chemical Process for the Methylene Blue Degradation by Natural Convective Nanofluid Flow over an Upright Cone.

An upstraight cone with nonisothermal surface velocity, temperature, and concentration was investigated using a numerical solution approach to simulate MHD, MB dye, and various nanofluid flows. Numerical evaluation of the flow field equation was carried out using an excellent finite difference method after it has been converted into a dimensionless form. Different heat transfer occurrences were observed depending on temperature, velocity, and concentration when using several types of nanofluids (TiO, Ag, Cu, and Al2O3Z3). The amount of MB dye that was degraded by the synthesized nanofluids under the influence of sunlight irradiation was 81.40 percent as a catalyst (carbon nanodots). The parametric analysis of various features of flow fields has been shown using graphs. It was observed that heat is generated from the cone during the sun light irradiation reaction, heat is transferred to MB dye containing nanofluids, and heat interacts with nanofluids and is involved in the chemical reaction with the assistance of electrons. As MB dye degrades in the absence of catalysts (carbon nanodots), it is only 52 percent effective. MB dye is degraded at 81.40 percent, then becomes stable, and takes 120 minutes to degrade in nanofluids containing MB dye with catalysts (carbon nanodots).

Fishery resource management with migratory prey harvesting in two zones- delay and stochastic approach.

In this work, we looked at a two-zone aquatic habitat where both prey and predators can access the zones. The prey alternates between two zones at random. The growth of prey in the absence of a predator is believed to be logistic in each zone. The inner steady state is determined. Around the interior steady state, the deterministic model's local and global stability is investigated. Furthermore, a stochastic stability study is performed in the neighbourhood of a positive steady state, using analytical estimates of population mean square fluctuations to investigate the system's dynamics in the presence of Gaussian white noise.

CB-Fake: A multimodal deep learning framework for automatic fake news detection using capsule neural network and BERT.

The progressive growth of today's digital world has made news spread exponentially faster on social media platforms like Twitter, Facebook, and Weibo. Unverified news is often disseminated in the form of multimedia content like text, picture, audio, or video. The dissemination of such false news deceives the public and leads to protests and creates troubles for the public and the government. Hence, it is essential to verify the authenticity of the news at an early stage before sharing it with the public. Earlier fake news detection (FND) approaches combined textual and visual features, but the semantic correlations between words were not addressed and many informative visual features were lost. To address this issue, an automated fake news detection system is proposed, which fuses textual and visual features to create a multimodal feature vector with high information content. The proposed work incorporates the bidirectional encoder representations from transformers (BERT) model to extract the textual features, which preserves the semantic relationships between words. Unlike the convolutional neural network (CNN), the proposed capsule neural network (CapsNet) model captures the most informative visual features from an image. These features are combined to obtain a richer data representation that helps to determine whether the news is fake or real. We investigated the performance of our model against different baselines using two publicly accessible datasets, Politifact and Gossipcop. Our proposed model achieves significantly better classification accuracy of 93% and 92% for the Politifact and Gossipcop datasets, respectively, compared to 84.6% and 85.6% for the SpotFake+ model.

Unraveling a cephalalgic quagmire from a cavern to a cave.

Headache in women in their late forties can be primary or secondary. We report a 48-year-old female with chronic slowly progressive left temporal headache for 1 year. She also had ipsilateral eye pain and facial numbness for 1 month, with restricted abduction in the left eye and diplopia. On neurological examination, she had isolated left abducent nerve palsy, with loss of corneal and conjunctival reflexes, localizing the pathology to the cavernous sinus or its adjacent structures. Anatomically, cranial nerves V and VI are in close proximity to each other in the region of Meckel's cave. In view of her age, insidious onset, progressive symptoms and clinical findings, the provisional diagnosis in this patient was a Meckel's cave tumor. Magnetic resonance (MR) imaging revealed a 2 cm × 2 cm × 1.7 cm enhancing dumb-bell-shaped mass lesion with mild restricted diffusion in the Meckel's cave projecting into cavernous sinus with alanine, myoinositol and glutamine peaks on MR spectroscopy. Intradural debulking was done; lesion was confirmed by histopathology and patient was cured of her symptoms. An algorithm for diagnosing this entity at the bedside is presented.

Vibration of symmetrically layered angle-ply cylindrical shells filled with fluid.

Vibrational behaviour of symmetric angle-ply layered circular cylindrical shell filled with quiescent fluid is presented. The equations of motion of cylindrical shell in terms of stress and moment resultants are derived from the first order shear deformation theory. Irrotational of inviscid fluid are expressed as the wave equation. These two equations are coupled. Strain-displacement relations and stress-strain relations are adopted into the equations of motion to obtain the differential equations with displacements and rotational functions. A system of ordinary differential equation is obtained in one variable by assuming the functions in separable form. Spline of order three is applied to approximate the displacement and rotational functions, together with boundary conditions, to get a generalised eigenvalue problem. The eigenvalue problem is solved for eigen frequency parameter and associate eigenvectors of spline coefficients. The study of frequency parameters are analysed using the parameters the thickness ratio, length ratio, angle-ply, properties of material and number of layers under different boundary conditions.

Combined aclidinium bromide and long-acting beta2-agonist for chronic obstructive pulmonary disease (COPD).

BACKGROUND: Several dual bronchodilator combinations of long-acting beta2-agonist (LABA) and long-acting muscarinic antagonist (LAMA) have been approved for treatment of stable chronic obstructive pulmonary disease (COPD). The current GOLD (Global Initiative for Chronic Obstructive Lung Disease) recommendations suggest the use of LABA/LAMA combinations in people with group B COPD with persistent symptoms, group C COPD with further exacerbations on LAMA therapy alone and group D COPD with or without inhaled corticosteroids (ICS). Fixed-dose combination (FDC) of aclidinium/formoterol is one of the approved LABA/LAMA therapies for people with stable COPD. OBJECTIVES: To assess the efficacy and safety of combined aclidinium bromide and long-acting beta2-agonists in stable COPD. SEARCH METHODS: We searched the Cochrane Airways Group Specialised Register (CAGR), ClinicalTrials.gov, World Health Organization (WHO) trials portal, United States Food and Drug Administration (FDA) and manufacturers' websites as well as the reference list of published trials up to 12 October 2018. SELECTION CRITERIA: Parallel-group randomised controlled trials (RCTs) assessing combined aclidinium bromide and LABAs in people with stable COPD. DATA COLLECTION AND ANALYSIS: We used standard methodological procedures expected by Cochrane for data collection and analysis. The primary outcomes were exacerbations requiring a short course of an oral steroid or antibiotic, or both; quality of life measured by a validated scale and non-fatal serious adverse events (SAEs). Where the outcome or study details were not reported, we contacted the study investigators or pharmaceutical company trial co-ordinators (or both) for missing data. MAIN RESULTS: We identified RCTs comparing aclidinium/formoterol FDC versus aclidinium, formoterol or placebo only. We included seven multicentre trials of four to 52 weeks' duration conducted in outpatient settings. There were 5921 participants, whose mean age ranged from 60.7 to 64.7 years, mostly men with a mean smoking pack-years of 46.4 to 61.3 of which 43.9% to 63.4% were current smokers. They had a moderate-to-severe degree of COPD with a mean postbronchodilator forced expiratory volume in one second (FEV1) between 50.5% and 61% of predicted normal and the baseline mean FEV1 of 1.23 L to 1.43 L. We assessed performance and detection biases as low for all studies whereas selection, attrition and reporting biases were either low or unclear.FDC versus aclidiniumThere was no evidence of a difference between FDC and aclidinium for exacerbations requiring steroids or antibiotics, or both (OR 0.95, 95% CI 0.71 to 1.27; 2 trials, 2156 participants; moderate-certainty evidence); quality of life measured by St George's Respiratory Questionnaire (SGRQ) total score (MD -0.92, 95% CI -2.15 to 0.30); participants with significant improvement in SGRQ score (OR 1.17, 95% CI 0.97 to 1.41; 2 trials, 2002 participants; moderate-certainty evidence); non-fatal SAE (OR 1.19, 95% CI 0.79 to 1.80; 3 trials, 2473 participants; moderate-certainty evidence); hospital admissions due to severe exacerbations (OR 0.62, 95% CI 0.29 to 1.29; 2 trials, 2156 participants; moderate-certainty evidence) or adverse events (OR 0.95, 95% CI 0.76 to 1.18; 3 trials, 2473 participants; moderate-certainty evidence). Compared with aclidinium, FDC improved symptoms (Transitional Dyspnoea Index (TDI) focal score: MD 0.37, 95% CI 0.07 to 0.68; 2 trials, 2013 participants) with a higher chance of achieving a minimal clinically important difference (MCID) of at least one unit improvement (OR 1.34, 95% CI 1.11 to 1.62; high-certainty evidence); the number needed to treat for an additional beneficial outcome (NNTB) being 14 (95% CI 9 to 39).FDC versus formoterolWhen compared to formoterol, combination therapy reduced exacerbations requiring steroids or antibiotics, or both (OR 0.78, 95% CI 0.62 to 0.99; 3 trials, 2694 participants; high-certainty evidence); may decrease SGRQ total score (MD -1.88, 95% CI -3.10 to -0.65; 2 trials, 2002 participants; low-certainty evidence; MCID for SGRQ is 4 units); increased TDI focal score (MD 0.42, 95% CI 0.11 to 0.72; 2 trials, 2010 participants) with more participants attaining an MCID (OR 1.30, 95% CI 1.07 to 1.56; high-certainty evidence) and an NNTB of 16 (95% CI 10 to 60). FDC lowered the risk of adverse events compared to formoterol (OR 0.78, 95% CI 0.65 to 0.93; 5 trials, 3140 participants; high-certainty evidence; NNTB 22). However, there was no difference between FDC and formoterol for hospital admissions, all-cause mortality and non-fatal SAEs.FDC versus placeboCompared with placebo, FDC demonstrated no evidence of a difference in exacerbations requiring steroids or antibiotics, or both (OR 0.82, 95% CI 0.60 to 1.12; 2 trials, 1960 participants; moderate-certainty evidence) or hospital admissions due to severe exacerbations (OR 0.55, 95% CI 0.25 to 1.18; 2 trials, 1960 participants; moderate-certainty evidence), although estimates were uncertain. Quality of life measure by SGRQ total score was significantly better with FDC compared to placebo (MD -2.91, 95% CI -4.33 to -1.50; 2 trials, 1823 participants) resulting in a corresponding increase in SGRQ responders who achieved at least four units decrease in SGRQ total score (OR 1.72, 95% CI 1.39 to 2.13; high-certainty evidence) with an NNTB of 7 (95% CI 5 to 12). FDC also improved symptoms measured by TDI focal score (MD 1.32, 95% CI 0.96 to 1.69; 2 studies, 1832 participants) with more participants attaining at least one unit improvement in TDI focal score (OR 2.51, 95% CI 2.02 to 3.11; high-certainty evidence; NNTB 4). There were no differences in non-fatal SAEs, adverse events and all-cause mortality between FDC and placebo.Combination therapy significantly improved trough FEV1 compared to aclidinium, formoterol or placebo. AUTHORS' CONCLUSIONS: FDC improved dyspnoea and lung function compared to aclidinium, formoterol or placebo, and this translated into an increase in the number of responders on combination treatment. Quality of life was better with combination compared to formoterol or placebo. There was no evidence of a difference between FDC and monotherapy or placebo for exacerbations, hospital admissions, mortality, non-fatal SAEs or adverse events. Studies reported a lower risk of moderate exacerbations and adverse events with FDC compared to formoterol; however, larger studies would yield a more precise estimate for these outcomes.

Effects of manufactured nano-copper on copper uptake, bioaccumulation and enzyme activities in cowpea grown on soil substrate.

Increased use of nanoparticles-based products in agriculture portends important implications for agriculture. Therefore, the impact of nano-copper particles (<25 nm and 60-80 nm) on Cu uptake, bioaccumulation (roots, leaves and seeds), activity of ascorbate peroxidase (APX), catalase (CAT), superoxide dismutase (SOD), glutathione reductase (GR), and lipid peroxidation in leaves and roots of Vigna unguiculata (cowpea) was studied. Plants were exposed to four levels (0, 125, 500 and 1000 mg/kg) of 25 nm or 60-80 nm nano-Cu for 65 days. Results indicated significant (P<.05) uptake of Cu at all nano-Cu levels compared to control, and bioaccumulation increased in seeds by at least 250%. Response of antioxidant enzymes to both nano-Cu types was concentration-dependent. Activity of APX and GR was enhanced in leaves and roots in response to both nano-Cu treatments in similar patterns compared to control. Both nano-Cu increased CAT activity in roots while SOD activity reduced in both leaves and roots. This shows that response of antioxidant enzymes to nano-Cu toxicity was organ-specific in cowpea. Malondialdehyde, a measure of lipid peroxidation, increased at 500 -1000 mg/kg of 25 nm nano-Cu in leaves by average of 8.4%, and 60-80 nm nano-Cu in root by 52.8%, showing particle-size and organ-dependent toxicity of nano-Cu. In conclusion, exposure of cowpea to nano-Cu treatments increased both the uptake and bioaccumulation of Cu, and also promoted the activity of APX and GR in root and leaf tissues of cowpea. Therefore, APX- and GR-activity level could be a useful predictive biomarker of nano-Cu toxicity in cowpea.

Multiple Hydrogen Bond Tethers for Grazing Formic Acid in Its Complexes with Phenylacetylene.

Complexes of phenylacetylene (PhAc) and formic acid (FA) present an interesting picture, where the two submolecules are tethered, sometimes multiply, by hydrogen bonds. The multiple tentacles adopted by PhAc-FA complexes stem from the fact that both submolecules can, in the same complex, serve as proton acceptors and/or proton donors. The acetylenic and phenyl π systems of PhAc can serve as proton acceptors, while the ≡C-H or -C-H of the phenyl ring can act as a proton donor. Likewise, FA also is amphiprotic. Hence, more than 10 hydrogen-bonded structures, involving O-H···π, C-H···π, and C-H···O contacts, were indicated by our computations, some with multiple tentacles. Interestingly, despite the multiple contacts in the complexes, the barrier between some of the structures is small, and hence, FA grazes around PhAc, even while being tethered to it, with hydrogen bonds. We used matrix isolation infrared spectroscopy to experimentally study the PhAc-FA complexes, with which we located global and a few local minima, involving primarily an O-H···π interaction. Experiments were corroborated by ab initio computations, which were performed using MP2 and M06-2X methods, with 6-311++G (d,p) and aug-cc-pVDZ basis sets. Single-point energy calculations were also done at MP2/CBS and CCSD(T)/CBS levels. The nature, strength, and origin of these noncovalent interactions were studied using AIM, NBO, and LMO-EDA analysis.

Inhibition of Redox Behaviors in Hierarchically Structured Manganese Cobalt Phosphate Supercapacitor Performance by Surface Trivalent Cations.

The stability and performance of supercapacitor devices are limited by the diffusion-controlled redox process occurring at materials' surfaces. Phosphate-based metal oxides could be effectively used as pseudocapacitors because of their polar nature. However, electrochemical energy storage applications of Mn-Co-based phosphate materials and their related kinetics studies have been rarely reported. In this work, we have reported a morphology-tuned Mn x Co3-x (PO4)2·8H2O (MCP) spinel compound synthesized by a one-step hydrothermal method. Detailed physical and chemical insights of the active material coated on the nickel substrate are examined by X-ray diffraction, field-emission scanning electron microscopy, field-emission transmission electron microscopy, and high-resolution X-ray photoelectron spectroscopy analyses. Physiochemical studies reveal that the well-defined redox behavior usually observed in Co2+/Ni2+ surface-terminated compounds is suppressed by reducing the divalent cation density with an increased Co3+ and Mn3+ surface states. A uniform and dense leaflike morphology observed in the MnCo2 phosphate compound with an increased surface area enhances the electrochemical energy storage performance. The high polar nature of P-O bonding formed at the surface leads to a higher rate of polarization and a very low relaxation time, resulting in a perfect square-shaped cyclic voltagram and triangular-shaped galvanostatic charge and discharge curve. We have achieved a highly pseudocapacitive MCP, and it can be used as a vital candidate in supercapacitor energy storage applications.

The borazine dimer: the case of a dihydrogen bond competing with a classical hydrogen bond.

Dimers of borazine were studied using matrix isolation infrared spectroscopy and ab initio quantum chemical calculations. Computations were performed at the MP2 and M06-2X levels of theory using the 6-311++G(d,p) and aug-cc-pVDZ basis sets for the various homodimers. At both levels of theory, an aligned stacked structure was found to be the global minimum, which was nearly isoenergetic to a parallel displaced structure. A T-shaped structure, where the N-H of one borazine pointed towards the N of the second borazine, was found to be a local minimum. In addition to these structures, a dihydrogen bonded structure, where the hydrogen attached to the nitrogen of borazine interacted with the hydrogen attached to the boron atom of another borazine, was also indicated. Experimentally, we observed the T-shaped dimer and the dihydrogen bonded dimer. This is one of the rare examples of experimental evidence for a dihydrogen bond, in a system other than in a metal hydride. These results for the borazine dimer were clearly different from the benzene dimer where the parallel displaced structure was found to be the global minimum followed by the T-shaped structure at the MP2/aug-cc-pVDZ level of theory. AIM, EDA and NBO analyses were carried out for all the structures to explore the nature of interactions.

Conformational Landscape of Tri-n-butyl Phosphate: Matrix Isolation Infrared Spectroscopy and Systematic Computational Analysis.

The conformations of tri-n-butyl phosphate (TBP) were studied using matrix isolation infrared spectroscopy and density functional theory (DFT) calculations. TBP was trapped in a N2 matrix using both effusive and supersonic sources, and its infrared spectra were recorded. The computational exploration of TBP is a very demanding problem to confront, due to the presence of a large multitude of conformations in TBP. To simplify the problem, computations were done on model compounds, dimethyl butyl phosphate (DMBP) and dibutyl methyl phosphate (DBMP), to systematically arrive at the conformations of TBP that are expected to contribute to its chemistry at room temperature. Some predictive rules seem to simplify this complex conformational landscape problem. The predictive rules that were formulated enabled us to search the relevant portion of the conformational topography of this molecule. The computations were performed at the B3LYP level of theory using the 6-31++G(d,p) basis set. Vibrational wavenumber calculations were also performed for the various conformers to assign the infrared features of TBP, trapped in solid N2 matrix.

H-π Landscape of the Phenylacetylene-HCl System: Does This Provide the Gateway to the Markovnikov Addition?

Non covalently bonded complexes of phenylacetylene-HCl were studied using matrix isolation infrared spectroscopy and ab initio calculations. Phenylacetylene (PhAc) is an interesting hydrogen bond precursor as it has multiple sites for weak interactions, and it was therefore considered worthwhile to study PhAc-HCl landscape. The interactions in PhAc-HCl were identified using the shifts in the infrared frequencies of the precursor molecules, as a result of complex formation. Our experiments unambiguously revealed spectral signatures of two types of H-π complexes, in both of which HCl was the proton donor. In one complex, the acetylenic π cloud (H-πAc) was the proton acceptor, while in the second, the role of the proton acceptor was played by the phenyl π cloud (H-πPh). The H-πAc and H-πPh complexes were evidenced by a 124 and 80 cm-1 red shift respectively, in the fundamental HCl stretch, relative to that of the uncomplexed HCl monomer. Ab initio calculations performed at M06-2X and MP2 level of theory using 6-311++G(d,p) and aug-cc-pVDZ basis functions indicated the H-πAc complex to be the global minimum and the H-πPh complex to be a local minimum; thus corroborating our experimental results. These conclusions were also confirmed by calculations at MP2/CBS and CCSD(T)/CBS limits. Interestingly, there were two isomers for the H-πAc complex, and it appears from an analysis of the charge densities, that one of the two isomers may serve as the gateway complex for the Markovnikov addition reaction. Computations identified a number of other minima, characterized by n-σ* and possibly Cl-π bonded structures, on the PhAc-HCl potential surface. AIM, NBO, and LMO-EDA analyses were also performed to characterize the non covalent interactions in the PhAc-HCl heterodimer.

Discerning Near-Isoergic Isomers. A Matrix Isolation Infrared and ab Initio Study of the Propargyl Alcohol Dimers.

This study reports the first infrared spectroscopic investigation of the dimers of propargyl alcohol (PA) using matrix isolation infrared spectroscopy and ab initio computations. Computations indicated a number of isomers for the dimer, with the two most stable structures being nearly isoergic. Interestingly, our matrix isolation experiments were able to discern both of these isomers, which were corroborated by computations performed at the M06-2X/6-311++G(d,p) level. Identifying these two isomers was significant, since the two most stable and near-isoergic isomers can be expected to play an important role in the structure of the propargyl alcohol ices, an understanding of which is of significant importance in the study of astrochemical environments. The global minimum structure differed from its near-isoergic local minimum, in the dimer architecture; the former making a three-point hydrogen-bonded contact, O-H···O, O-H···π, and C-H···π, and the latter having two. The global minimum had been observed in molecular beam experiments, though not the near-isoergic local minimum. In both isomers, the propargyl alcohol monomer units were in their gauche conformation. AIM and NBO analyses were also performed to understand the nature of interaction in the dimers. The results of this study may well have significant implications in interpreting the PA spectra in astrochemical environments.

Matrix Isolation Infrared and Ab Initio Study of the Interaction of N-Heterocyclic Carbene with Water and Methanol: A Case Study of a Strong Hydrogen Bond.

This study reports, for the first time, the experimental study of the hydrogen-bonded complexes of H2O and MeOH with 1,3-dimethylimidazol-2-ylidene, which is a dimethyl-substituted N-heterocyclic carbene, using matrix isolation infrared spectroscopy. The hydrogen bond was found to be established between the carbene carbon and the hydrogen in the O-H group of H2O or MeOH. The hydrogen-bonded complexes of N-heterocyclic carbenes are significantly stronger than many conventional hydrogen-bonded systems, as is evidenced by the large red shifts observed in the infrared frequencies of complexed H2O and MeOH. The experimental results were corroborated by computations performed at MP2 and M06-2X levels of theory, using 6-311++G(d,p) and aug-cc-pVDZ basis sets, which indicated large interaction energies (∼9 kcal mol-1) for these complexes. Single-point calculations at the CCSD level of theory were also performed. Atoms-in-molecules (AIM), NBO, and LMOEDA analyses were also performed to understand the nature of the intermolecular interactions in these complexes. The dominant interaction was the electron delocalization from the carbene carbon to the σ* orbital of O-H of H2O or MeOH.

Sudden Appearance of Indurated Erythematous Plaques on a Man's Face.

Rosacea fulminans (RF), previously known as pyoderma faciale, is a rare presentation of rosacea mostly seen in young women. RF is seen very rarely in men. We present below a case of a fifty-year-old male who presented with RF and was successfully treated with a combination of corticosteroids and isotretinoin.

Does borazine-water behave like benzene-water? A matrix isolation infrared and ab initio study.

Borazine is isoelectronic with benzene and is popularly referred to as inorganic benzene. The study of non-covalent interactions with borazine and comparison with its organic counterpart promises to show interesting similarities and differences. The motivation of the present study of the borazine-water interaction, for the first time, stems from such interesting possibilities. Hydrogen-bonded complexes of borazine and water were studied using matrix isolation infrared spectroscopy and quantum chemical calculations. Computations were performed at M06-2X and MP2 levels of theory using 6-311++G(d,p) and aug-cc-pVDZ basis sets. At both the levels of theory, the complex involving an N-H⋯O interaction, where the N-H of borazine serves as the proton donor to the oxygen of water was found to be the global minimum, in contrast to the benzene-water system, which showed an H-π interaction. The experimentally observed infrared spectra of the complexes corroborated well with our computations for the complex corresponding to the global minimum. In addition to the global minimum, our computations also located two local minima on the borazine-water potential energy surface. Of the two local minima, one corresponded to a structure where the water was the proton donor to the nitrogen of borazine, approaching the borazine ring from above the plane of the ring; a structure that resembled the global minimum in the benzene-water H-π complex. The second local minimum corresponded to an interaction of the oxygen of water with the boron of borazine, which can be termed as the boron bond. Clearly the borazine-water system presents a richer landscape than the benzene-water system.

Phase transition kinetics and surface binding states of methylammonium lead iodide perovskite.

We have presented a detailed analysis of the phase transition kinetics and binding energy states of solution processed methylammonium lead iodide (MAPbI3) thin films prepared at ambient conditions and annealed at different elevated temperatures. It is the processing temperature and environmental conditions that predominantly control the crystal structure and surface morphology of MAPbI3 thin films. The structural transformation from tetragonal to cubic occurs at 60 °C with a 30 minute annealing time while the 10 minute annealed films posses a tetragonal crystal structure. The transformed phase is greatly intact even at the higher annealing temperature of 150 °C and after a time of 2 hours. The charge transfer interaction between the Pb 4f and I 3d oxidation states is quantified using XPS.

Hydrogen-Bonded Complexes of Phenylacetylene-Acetylene: Who is the Proton Donor?

Hydrogen-bonded complexes of C2H2 and phenylacetylene (PhAc) were studied using matrix isolation infrared spectroscopy and quantum chemical computations. Both C2H2 and PhAc, being potential proton donors, the question arises as to which of the two species would be the proton donor in the PhAc-C2H2 complex; a question that this work primarily addresses. The molecular structures, vibrational frequencies, and interaction energies of the PhAc-C2H2 complexes were calculated at the M06-2X and MP2 levels of theory, employing both 6-311++G(d,p) and aug-cc-pVDZ basis sets. At the M06-2X/aug-cc-pVDZ level, two nearly isoenergetic complexes (BSSE corrected) were indicated to be the global minima; one a C-H···π complex, where C2H2 served as a proton donor to the phenyl π-system in PhAc, and the other a C-H···π complex, where C2H2 served as a proton donor to the acetylene π-system in PhAc. Of the two, only the second complex was identified in the matrix, evidenced by a characteristic large shift in the ≡C-H stretch of C2H2. Experiments were also performed using PhAc deuterated at the acetylene hydrogen (PhAcD) to study the isotopic effects on the vibrational spectra of complexes. The isotopic studies further confirmed the structure of the complex trapped in the matrix, thereby presenting unambiguous evidence that C2H2 served as the proton donor to the acetylene π-system of PhAc. The theory of atoms-in-molecules (AIM), energy decomposition (EDA), and natural bond orbital (NBO) analysis were performed to understand the nature of the interactions involved in the complexes.

Spectroscopic investigation of 4-nitro-3-(trifluoromethyl)aniline, NBO analysis with 4-nitro-3-(trichloromethyl)aniline and 4-nitro-3-(tribromomethyl)aniline.

The Fourier transform infrared (FT-IR) and FT-Raman spectra of 4-nitro-3-(trifluoromethyl)aniline (NTFA) were recorded in the regions 4000-400 cm(-1) and 3500-100 cm(-1), respectively. Utilizing the observed FT-IR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compounds was carried out. Extensive studies on the vibrational, structural, thermodynamic characteristics as well as the electronic properties of NTFA were carried out using ab initio and DFT methods. In this kind of systems, the position of the substituent group in the benzene ring as well as its electron donor-acceptor capabilities play a very important role on the molecular and electronic properties. The values of the total dipole moment (µ) and the first order hyperpolarizability (ß) were computed using B3LYP/6-311++G(d,p) and B3LYP/6-311G(d) calculations. The Mulliken's charges, the natural bonding orbital (NBO) analysis on 4-nitro-3-(trifluoromethyl)aniline, 4-nitro-3-(trichloromethyl)aniline and 4-nitro-3-tribromomethyl)aniline were carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. Thermodynamic functions of the investigated molecule were also computed. The calculated HOMO-LUMO energies show that charge transfer occurs in the molecule. The influence of fluorine, amino and nitro group on the geometry of benzene and its normal modes of vibrations has also been discussed.