Scytonin,a novel cyanobacterial photoprotective pigment: calculations of Raman spectroscopic biosignatures

Experimental studies have shown that chemical vapor decomposition method by using C₂H₂/C₂H₄ as carbon source could dramatically decrease the defects in prepared CNT. However, the inherent mechanism with regards to reduction of defects is quite unclear. In the present paper, density functional theory is used to study the healing process of CNT with divacancy defect by C₂H₂/C₂H₄ molecule. The healing processes undergo three evolution steps: (i) the chemisorption of the first C₂H₂/C₂H₄ molecule on defective CNT; (ii) the insertion of C atoms from C₂H₂/C₂H₄ molecule into defective CNT; (iii) the removal of the H atoms on CNT, forming perfect CNT. The estimated adsorption energy barrier of C₂H₂/C₂H₄ molecules on defective CNT is within the range from 1.10 to 1.63 eV, and the eventual formation of CNT is strongly exothermic (4.40/4.54 eV in (8, 0) CNT). In light of the unique conditions of CNT synthesis, i.e., high temperature in a closed container, such healing processes could most likely take place. Therefore, we propose that during CNT synthesis procedures, both C₂H₂ and C₂H₄ could act as a carbon source and the defect healer.

A Gaussian-3 theoretical study of the alkylthio radicals and their anions: structures, thermochemistry, and electron affinities

The optimized geometries, electron affinities, and dissociation energies of the alkylthio radicals have been determined with the higher level of the Gaussian-3(G3) theory. The geometries are fully optimized and discussed. The reliable adiabatic electron affinities with ZPVE correction have been predicted to be 1.860 eV for the methylthio radical, 1.960 eV for the ethylthio radical, 1.980 and 2.074 eV for the two isomers (n-C₃H₇S and i-C₃H₇S) of the propylthio radical, 1.991, 2.133 and 2.013 eV for the three isomers (n-C₄H₉S, t-C₄H₉S, and i-C₄H₉S) of the butylthio radical, and 1.999, 2.147, 2.164, and 2.059 eV for the four isomers (n-C₅H₁₁S, b-C₅H₁₁S, c-C₅H₁₁S, and d-C₅H₁₁S) of the pentylthio radical, respectively. These corrected EA_ad values for the alkylthio radicals are in good agreement with available experiments, and the average absolute error of the G3 method is 0.041 eV. The dissociation energies of S atom from neutral C_nH_2n+1S (n?=?1–5) and S^- from corresponding anions C_nH_2n+1S^- species have also been estimated respectively to examine their relative stabilities.     

Reconnoitring the current characteristics of the double C<Subscript>20</Subscript> fullerene molecular device in two probe configuration

It is worth remarking that the C₂₀ cage like isomer has been the topic of concentrated theoretical research. C₂₀ single fullerene molecular devices gained a lot of popularity in the field of nano research due to their superlative doping dependent conductive properties. In this work, the double fullerene device has been considered. Here double fullerene molecular junction is created when two C₂₀ fullerene molecules, one in pristine form and other in doped form, are positioned between gold electrodes. Doping was done firstly by second period elements, boron, nitrogen, oxygen, and fluorine and then by group 14 tetragens, silicon, germanium, tin, and lead. For both the cases current characteristics were investigated. Superior conductivity was observed in the boron doped double C₂₀ molecular device while the fluorine doped device was the least conducting. Further for group 14 doping, the silicon doped double C₂₀ device showed maximum current carrying feature, whereas, least value of current was noted in tin doped C₂₀ device.     

Hydrogen Sulfide Endothelin-Induced Myocardial Hypertrophy in Rats and the Mechanism Involved

The aim of the study was to evaluate the clinical efficacy of hydrogen sulfide (H₂S) treatment on the endothelin-induced cardiac hypertrophy. Sixty-four adult male rats, weighing from 180 to 200 g, were randomly divided into four groups: ten in normal group, ten in sham group, 44 in model group established by inducing the myocardial hypertrophy with endothelin. The myocardial hypertrophy model rats were randomly divided into two groups: 22 in the simple myocardial hypertrophy model group and 22 in the H₂S treatment group. Rats in normal group were given 2 ml pure water by gavage per day, those in the sham group and simple cardiac hypertrophy model group were given 2 ml of saline by gavage per day, and rats in the pure cardiac hypertrophy with H₂S treatment were given intraperitoneal injections of 2 ml NaHS saline per day for a period of 4 weeks. Left ventricular mass index, myocyte hypertrophy, volume fraction of myocardial interstitial collagen, myocardial hydroxyproline content and other indicators of cardiac hypertrophy were observed after 4 weeks. (1) There were significant differences on the ventricular mass between the treatment group and the cardiac hypertrophy group: The left ventricular mass decreased 21.4 % and the left ventricular mass index decreased 5.97 % (P < 0.05; (2) the smallest cardiomyocytes diameter and cardiomyocytes cross-sectional area decreased 12.5 and 10.8 %, respectively (P < 0.05) in the treatment group compared to the cardiac hypertrophy group; (3) the volume fraction of myocardial interstitial collagen and the myocardial hydroxyproline content decreased 22.3 and 31.3 % in treatment group compared with the cardiac hypertrophy group, respectively (P < 0.05). H₂S had a good clinical efficacy in reducing left ventricular mass fraction and myocardial collagen levels, improving myocardial hypertrophy and decrease myocardial fibrosis. It is worthy for further clinical studies.     

Fluorination of BC3 nanotubes: DFT studies

We have studied the adsorption of atomic and molecular fluorines on a BC₃ nanotube by using density functional calculations. It was found that the adsorption of atomic fluorine on a C atom of the tube surface is energetically more favorable than that on a B atom by about 0.97 eV. The adsorption of atomic fluorine on both C and B atoms significantly affects the electronic properties of the BC₃ tube. The HOMO-LUMO energy gap is considerably reduced from 2.37 to 1.50 and 1.14 eV upon atomic F adsorption on B and C atoms, respectively. Molecular fluorine energetically tends to be dissociated on B atoms of the tube surface. The associative and dissociative adsorption energies of F₂ were calculated to be about ?0.42 and ?4.79 eV, respectively. Electron emission density from BC₃ nanotube surface will be increased upon both atomic and molecular fluorine adsorptions due to work function decrement.     

Theoretical study of the electronic properties of fluorographene

First-principles calculations were performed for fluorine-decorated graphene (fluorographene). Three different hexagonal clusters were used—circular (C₂₄H₁₂), triangular (C₂₃H₁₀) and rectangular (C₂₄H₁₂)—and the fluorine atoms were randomly distributed in the mesh. Graphene is structurally stable in the three geometries, but fluorographene stability is only attained for the circular and triangular clusters. Gaps of the circular graphene and the corresponding fluorographene are 2.94 and 1.13 eV, respectively; in the triangular case, the values are zero and 0.47 eV. Both the circular and triangular structures show a transition from ionic to covalent character.     

Oxygen transfer as a tool for fine-tuning recombinant protein production by <Emphasis Type="Italic">Pichia pastoris</Emphasis> under glyceraldehyde-3-phosphate dehydrogenase promoter

Effects of oxygen transfer on recombinant protein production by Pichia pastoris under glyceraldehyde-3-phosphate dehydrogenase promoter were investigated. Recombinant glucose isomerase was chosen as the model protein. Two groups of oxygen transfer strategies were applied, one of which was based on constant oxygen transfer rate where aeration rate was Q _O/V = 3 and 10 vvm, and agitation rate was N = 900 min^?1; while the other one was based on constant dissolved oxygen concentrations, C _DO = 5, 10, 15, 20 and 40 % in the fermentation broth, by using predetermined exponential glucose feeding with μ _o = 0.15 h^?1. The highest cell concentration was obtained as 44 g L^?1 at t = 9 h of the glucose fed-batch phase at C _DO = 20 % operation while the highest volumetric and specific enzyme activities were obtained as 4440 U L^?1 and 126 U g^?1 cell, respectively at C _DO = 15 % operation. Investigation of specific enzyme activities revealed that keeping C _DO at 15 % was more advantageous with an expense of relatively higher by-product formation and lower specific cell growth rate. For this strategy, the highest oxygen transfer coefficient and oxygen uptake rate were K _L a = 0.045 s^?1 and OUR = 8.91 mmol m^?3 s^?1, respectively.     

Daily variations in the thermoregulatory behaviors of naked neck broilers in an equatorial semi-arid environment

The aim of this study was to evaluate the daily variations in the thermoregulatory behavior of 4- to 6-week-old naked neck broilers (Label Rouge) in an equatorial semi-arid environment. A total of 220 birds were monitored for 5 days starting at 0600 hours and ending at 1800 hours. The period of observation was divided into classes of hours (C _H). The observed behaviors were as follows: feed and water intake, wing-spreading, sitting or lying, and beak-opening. A total of 14,300 behavioral data values were registered. In C _H 2 (0900 hours to 1100 hours) and 3 (1200 hours to 1500 hours), the greatest average body surface temperature was recorded (34.67?±?0.25 °C and 35.12?±?0.22 °C, respectively). The C _H had an effect on the exhibition of all behaviors with the exception of the water intake behavior. Feed intake was more frequent in C _H 1 (0600 hours to 0800 hours) and 4 (1600 hours to 1800 hours). In C _H 2 and 3, the highest frequency of sitting or lying behavior was observed. Beak-opening and wing-spreading behaviors occurred more frequently in C _H 3 where the body surface temperature (35.12?±?0.22 °C), radiant heat load (519.38?±?2.22 W m^?2), and enthalpy (82.74?±?0.36 kJ kg^?1 of dry air) reached maximum recorded averages. Thus, it can be concluded that naked neck broilers adjust their behavior in response to daily variations in the thermal environment. Wing-spreading and beak-opening behaviors are important adaptive responses to the thermal challenges posed by the equatorial semi-arid environment.     

Biodegradation of microcystin-LR and-RR by a novel microcystin-degrading bacterium isolated from Lake Taihu

Microcystin-LR (MC-LR) and microcystin-RR (MC-RR) are the two most common microcystins (MCs) present in fresh water posing a direct threat to public health because of their hepatotoxicity. A novel MC-degrading bacterium designated MC-LTH1 capable of degrading MC-LR and -RR was isolated, and the degradation rates and mechanisms of MC-LR and -RR for this bacterium were investigated. The bacterium was identified as Bordetella sp. and shown to possess a homologous mlrA gene responsible for degrading MCs. To the best of our knowledge, this is the first report of mlrA gene detection in Bordetella species. MC-LR and -RR were completely degraded separately at rates of 0.31 mg/(L h) and 0.17 mg/(L h). However, the degradation rates of MC-LR and -RR decreased surprisingly to 0.27 mg/(L h) and 0.12 mg/(L h), respectively, when both of them were simultaneously present. Degradation products were identified by high performance liquid chromatography coupled with time-of-flight mass spectrometry. Adda (m/z 332.2215, C₂₀H₂₉NO₃) commonly known as a final product of MC degradation by isolated bacteria was detected as an intermediate in this study. Linearized MC-LR (m/z 1013.5638, C₄₉H₇₆N₁₀O₁₃), linearized MC-RR (m/z 1056.4970, C₄₉H₇₇N₁₃O₁₃), and tetrapeptide (m/z 615.3394, C₃₂H₄₆N₄O₈) were also detected as intermediates. These results indicate that the bacterial strain MC-LTH1 is quite efficient for the detoxification of MC-LR and MC-RR, and possesses significant bioremediation potential.     

Time-dependent density functional theory study on the electronic excited-state hydrogen bonding of the chromophore coumarin 153 in a room-temperature ionic liquid

In the present work, in order to investigate the electronic excited-state intermolecular hydrogen bonding between the chromophore coumarin 153 (C153) and the room-temperature ionic liquid N,N-dimethylethanolammonium formate (DAF), both the geometric structures and the infrared spectra of the hydrogen-bonded complex C153–DAF⁺ in the excited state were studied by a time-dependent density functional theory (TDDFT) method. We theoretically demonstrated that the intermolecular hydrogen bond C₁?=?O₁···H₁–O₃ in the hydrogen-bonded C153–DAF⁺ complex is significantly strengthened in the S₁ state by monitoring the spectral shifts of the C=O group and O–H group involved in the hydrogen bond C₁?=?O₁···H₁–O₃. Moreover, the length of the hydrogen bond C₁?=?O₁···H₁–O₃ between the oxygen atom and hydrogen atom decreased from 1.693 Å to 1.633 Å upon photoexcitation. This was also confirmed by the increase in the hydrogen-bond binding energy from 69.92 kJ mol^?1 in the ground state to 90.17 kJ mol^?1 in the excited state. Thus, the excited-state hydrogen-bond strengthening of the coumarin chromophore in an ionic liquid has been demonstrated theoretically for the first time.     

The effect of C-vacancy on hydrogen storage and characterization of H2 modes on Ti functionalized C60 fullerene A first principles study

Density functional theory calculations were performed to examine the effect of a C vacancy on the physisorption of H₂ onto Ti-functionalized C₆₀ fullerene when H₂ is oriented along the x-, y-, and z-axes of the fullerene. The effect of the C vacancy on the physisorption modes of H₂ was investigated as a function of H₂ binding energy within the energy window (?0.2 to ?0.6 eV) targeted by the Department of Energy (DOE), and as functions of a variety of other physicochemical properties. The results indicate that the preferential orientations of H₂ in the defect-free (i.e., no C vacancy) C₆₀TiH₂ complex are along the x- and y-axes of C₆₀ (with adsorption energies of ?0.23 and ?0.21 eV, respectively), making these orientations the most suitable ones for hydrogen storage, in contrast to the results obtained for defect-containing fullerenes. The defect-containing (i.e., containing a C vacancy) C₅₉TiH₂ complex do not exhibit adsorption energies within the targeted energy range. Charge transfer occurs from Ti 3d to C 2p of the fullerene. The binding of H₂ is dominated by the pairwise support–metal interaction energy E(i)^Cn...Ti, and the role of the fullerene is not restricted to supporting the metal. The C vacancy enhances the adsorption energy of Ti, in contrast to that of H₂. A significant reduction in the energy gap of the pristine C₆₀ fullerene is observed when TiH₂ is adsorbed by it. While the C _n fullerene readily participates in nucleophilic processes, the adjacent TiH₂ fragment is available for electrophilic processes.

Methylobacterium pseudosasae sp. nov., a pink-pigmented, facultatively methylotrophic bacterium isolated from the bamboo phyllosphere

A pink-pigmented, Gram negative, aerobic, facultatively methylotrophic bacterium, strain BL44^T, was isolated from bamboo leaves and identified as a member of the genus Methylobacterium. Phylogenetic analysis based on 16S rRNA gene sequences showed similarity values of 98.7–97.0 % with closely related type strains and showed highest similarity to Methylobacterium zatmanii DSM 5688^T (98.7 %) and Methylobacterium thiocyanatum DSM 11490^T (98.7 %). Methylotrophic metabolism in this strain was confirmed by PCR amplification and sequencing of the mxaF gene coding for the α-subunit of methanol dehydrogenase. Strain BL44^T produced three known quorum sensing signal molecules with similar retention time to C₈, C₁₀ and C₁₂-HSLs when characterized by GC–MS. The fatty acid profiles contained major amounts of C_18:1 ω7c, iso-3OH C_17:0 and summed feature 3 (C_16:1 ω7c and/or iso-C_15:0 2-OH), which supported the grouping of the isolate in the genus Methylobacterium. The DNA G+C content was 66.9 mol%. DNA relatedness of the strain BL44^T to its most closely related strains ranged from 12–43.3 %. On the basis of the phenotypic, phylogenetic and DNA–DNA hybridization data, strain BL44^T is assigned to a novel species of the genus Methylobacterium for which the name Methylobacterium pseudosasae sp. nov. is proposed (type strain BL44^T = NBRC 105205^T = ICMP 17622^T).     

Theoretical study of the interaction between X (H,F) and graphene

This study investigates the interaction between X (X = H and F) and graphene C₅₄H₁₈ (D_6 h), and the potential energy surface of the graphene radical. The calculations on the structures and energies are further discussed thermodynamically and kinetically using the density function theory method at the B3LYP/6-31G (d) level. Our findings show that there are four distinct isomers of C₅₄H₁₈–X. C₅₄H₁₈–H² and C₅₄H₁₈–F⁴ are the most stable isomers in their own systems. In addition, the transition states, as well as reaction pathways of H transferring between different key points on representative patch, are given to explore the possible reaction mechanism. Finally, the stability of C₅₄H₁₈–X₂ is discussed through the density functional theory.     

Spectroscopic Studies on the Interaction of Fluorine Containing Triazole with Bovine Serum Albumin

The binding of one fluorine including triazole (C₁₀H₉FN₄S, FTZ) to bovine serum albumin (BSA) was studied by spectroscopic techniques including fluorescence spectroscopy, UV–Vis absorption, and circular dichroism (CD) spectroscopy under simulative physiological conditions. Fluorescence data revealed that the fluorescence quenching of BSA by FTZ was the result of forming a complex of BSA–FTZ, and the binding constants (K _a) at three different temperatures (298, 304, and 310 K) were 1.516?×?10⁴, 1.627?×?10⁴, and 1.711?×?10⁴?mol L^?1, respectively, according to the modified Stern–Volmer equation. The thermodynamic parameters ΔH and ΔS were estimated to be 7.752 kJ mol^?1 and 125.217 J?mol^?1?K^?1, respectively, indicating that hydrophobic interaction played a major role in stabilizing the BSA–FTZ complex. It was observed that site I was the main binding site for FTZ to BSA from the competitive experiments. The distance r between donor (BSA) and acceptor (FTZ) was calculated to be 7.42 nm based on the Förster theory of non-radioactive energy transfer. Furthermore, the analysis of fluorescence data and CD data revealed that the conformation of BSA changed upon the interaction with FTZ.     

Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets,Comets and Interstellar Organic Synthesis

Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH₃ (ammonia) and C₂H₂ (acetylene) within the context Jupiter’s atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH₃CN (acetonitrile), CH₃CH = N-N = CHCH₃ (acetaldazine), CH₃CH = N-NH₂ (acetaldehyde hydrazone), C₂H₅NH₂ (ethylamine), CH₃NH₂ (methylamine) and C₂H₄ (ethene) in the photolysis of NH₃/C₂H₂ mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH₃CH = N-N = CHCH₃ does not explain all of the results obtained in this study. The formation of CH₃CH = N-N = CHCH₃ by a radical combination reaction of CH₃CH = N? was shown in this work to be inconsistent with other experiments where the CH₃CH = N? radical is thought to form but where no CH₃CH = N-N = CHCH₃ was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH₃CH = N-N = CHCH₃ formation involving nucleophilic reaction between N₂H₄ and CH₃CH = NH is advanced.     

Inhalation pressure distributions for medical gas mixtures calculated in an infant airway morphology model

A numerical pressure loss model previously used for adult human airways has been modified to simulate the inhalation pressure distribution in a healthy 9-month-old infant lung morphology model. Pressure distributions are calculated for air as well as helium and xenon mixtures with oxygen to investigate the effects of gas density and viscosity variations for this age group. The results indicate that there are significant pressure losses in infant extrathoracic airways due to inertial effects leading to much higher pressures to drive nominal flows in the infant airway model than for an adult airway model. For example, the pressure drop through the nasopharynx model of the infant is much greater than that for the nasopharynx model of the adult; that is, for the adult-versus-child the pressure differences are 0.08 cm H₂O versus 0.4 cm H₂O, 0.16 cm H₂O versus 1.9 cm H₂O and 0.4 cm H₂O versus 7.7 cm H₂O, breathing helium–oxygen (78/22%), nitrogen–oxygen (78/22%) and xenon–oxygen (60/40%), respectively. Within the healthy lung, viscous losses are of the same order for the three gas mixtures, so the differences in pressure distribution are relatively small.     

Monte Carlo study of sI hydrogen hydrates

In this study, we perform grand canonical Monte Carlo simulations to evaluate the hydrogen storage capacity of structure I (sI) hydrogen hydrates at pressures up to 500 MPa. Initially, we calculate the upper limit of H₂ content of sI hydrates by studying the hypothetical sI hydrate, where H₂ is the single guest component. It is found that the storage capacity of the hypothetical pure H₂ sI hydrate could reach 3.5 wt% at 500 MPa and 274 K. Depending on pressure, the large cavities of the pure H₂ hydrate can accommodate up to three H₂ molecules while the small ones are singly occupied at most, even at pressures as high as 500 MPa, without any double occupancy being observed. Subsequently, the binary H₂–ethylene oxide (EO) hydrate is examined. In this case, the large cavities are occupied by a single EO molecule while the small cavities can accommodate at most a single H₂ molecule. Such configuration results in a maximum H₂ content of only 0.37 wt%. The hydrogen storage capacity does not improve significantly even in case when EO is replaced by a component with smaller molecular weight.