Ab Initio Study of Fine and Hyperfine Interactions in Triplet POH

Phosphorous-containing molecules have a great relevance in prebiotic chemistry in view of the fact that phosphorous is a fundamental constituent of biomolecules, such as RNA, DNA, and ATP. Its biogenic importance has led astrochemists to investigate the possibility that P-bearing species could have formed in the interstellar medium (ISM) and subsequently been delivered to early Earth by rocky bodies. However, only two P-bearing molecules have been detected so far in the ISM, with the chemistry of interstellar phosphorous remaining poorly understood. Here, in order to shed further light on P-carriers in space, we report a theoretical spectroscopic characterisation of the rotational spectrum of POH in its 3A″ ground electronic state. State-of-the-art coupled-cluster schemes have been employed to derive rotational constants, centrifugal distortion terms, and most of the fine and hyperfine interaction parameters, while the electron spin–spin dipolar coupling has been investigated using the multi-configuration self-consistent-field method. The computed spectroscopic parameters have been used to simulate the appearance of triplet POH rotational and ro-vibrational spectra in different conditions, from cold to warm environments, either in gas-phase experiments or in molecular clouds. Finally, we point out that the predicted hyperfine structures represent a key pattern for the recognition of POH in laboratory and interstellar spectra.     

Skeletal Torsion Tunneling and Methyl Internal Rotation: The Coupled Large Amplitude Motions in Phenyl Acetate

The rotational spectrum of phenyl acetate, CH₃COOC₆H₅, is measured using a free jet absorption millimeter-wave spectrometer in the range from 60 to 78 GHz and two pulsed jet Fourier transform microwave spectrometers covering a total frequency range from 2 to 26.5 GHz. The features of two large amplitude motions, the methyl group internal rotation and the skeletal torsion of the CH₃COO group with respect to the phenyl ring C₆H₅ (tilted at about 70°), characterize the spectrum. The vibrational ground state is split into four widely spaced sublevels, labeled as A0, E0, A1, and E1, each of them with its set of rotational transitions and with additional interstate transitions. A global fit of the line frequencies of the four sublevels leads to the determination of 51 spectroscopic parameters, including the ΔE_A0/A1 and ΔE_E0/E1 vibrational splittings of ~36.4 and ~33.5 GHz, respectively. The V₃ barrier to methyl internal rotation (~136 cm⁻¹) and the skeletal torsion B₂ barrier to the orthogonality of the two planes (~68 cm⁻¹) are deduced.     

The pure rotational spectrum of NaCH3 ( )

The pure rotational spectrum of NaCH₃ and NaCD₃ in their states has been recorded using millimeter/sub-mm direct absorption techniques in the 300–510 GHz range. This work is the first gas-phase detection of sodium monomethyl, which was created by the reaction of sodium vapor with tetramethyl tin. Ten rotational transitions were measured for NaCH₃ for the K=0 through K=5 components and, in select cases, up to K=10, and four transitions (K=0–7) for NaCD₃. Rotational constants have been accurately determined for both isotopomers, suggesting a sodium–carbon bond length of 2.30 Å and an H–C–H bond angle of 107.3°.     

Depolarization Ratio of the ν1 Raman Band of Pure CH4 and Perturbed by N2 and CO2

In this work, the effect of nitrogen and carbon dioxide on the depolarization ratio of the ν₁ band of methane in the pressure range of 0.1–5 MPa is studied. A high-sensitivity single-pass Raman spectrometer was used to obtain accurate results. Moreover, we took into account the overlap of the ν₁ band by the ν₃ and ν₂ + ν₄ bands using the simulation of their spectra. The depolarization ratio of the ν₁ band in pure methane is within 0–0.001, and the effect of nitrogen and carbon dioxide on this parameter is negligible in the indicated pressure range. The obtained results are useful for correct simulation of the Raman spectrum of methane at different pressures, which is necessary to improve the accuracy of gas analysis methods using Raman spectroscopy.     

Synthesis of Prebiotic Glycerol in Interstellar Ices

Contemporary mechanisms for the spontaneous formation of glycerol have not been able to explain its existence on early Earth. The exogenous origin and delivery of organic molecules to early Earth presents an alternative route to their terrestrial in situ formation since biorelevant molecules like amino acids, carboxylic acids, and alkylphosphonic acids have been recovered from carbonaceous chondrites. Reported herein is the first in situ identification of glycerol, the key building block of all cellular membranes, formed by exposure of methanol‐based — interstellar model ices to ionizing radiation in the form of energetic electrons. These results provide compelling evidence that the radiation‐induced formation of glycerol in low‐temperature interstellar model ices is facile. Synthesized on interstellar grains and eventually incorporated into the “building material” of solar systems, biorelevant molecules such as glycerol could have been dispensed to habitable planets such as early Earth by comets and meteorites.     

Characterisation of Engineered Nanomaterials in Nano-Enabled Products Exhibiting Priority Environmental Exposure

Analytical limitations have constrained the determination of nanopollution character from real-world sources such as nano-enabled products (NEPs), thus hindering the development of environmental safety guidelines for engineered nanomaterials (ENMs). This study examined the properties of ENMs in 18 commercial products: sunscreens, personal care products, clothing, and paints—products exhibiting medium to a high potential for environmental nanopollution. It was found that 17 of the products contained ENMs; 9, 3, 3, and 2 were incorporated with nTiO₂, nAg, binaries of nZnO + nTiO₂, and nTiO₂ + nAg, respectively. Commonly, the nTiO₂ were elongated or angular, whereas nAg and nZnO were near-spherical and angular in morphology, respectively. The size ranges (width × length) were 7–48 × 14–200, 34–35 × 37–38, and 18–28 nm for nTiO₂, nZnO, and nAg respectively. All ENMs were negatively charged. The total concentration of Ti, Zn, and Ag in the NEPs were 2.3 × 10⁻⁴–4.3%, 3.4–4.3%, and 1.0 × 10⁻⁴–11.3 × 10⁻³%, respectively. The study determined some key ENM characteristics required for environmental risk assessment; however, challenges persist regarding the accurate determination of the concentration in NEPs. Overall, the study confirmed NEPs as actual sources of nanopollution; hence, scenario-specific efforts are recommended to quantify their loads into water resources.     

On the equilibrium structure of MgC2 and AlC2

In order to find such unknown molecules as MgC₂ and AlC₂ in interstellar space, accurate calculations to determine the equilibrium structures of these molecules were carried out. The ab initio MCSCF and MRSDCI methods were employed in the calculations. MgNC whose rotational constant has been observed was used to check the reliability of the computational scheme. The predicted geometrical structures of MgC₂ and AlC₂ were equilateral triangles and their rotational constants were A_e = 51.55, B_e = 11.52 and C_e = 9.413 GHz for MgC₂ and A_e = 50.76, B_e = 12.00 and C_e = 9.705 GHz for AlC₂.     

Hydrogen Bonding in the Dimer and Monohydrate of 2-Adamantanol: A Test Case for Dispersion-Corrected Density Functional Methods

Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterized using broadband chirped-pulse microwave spectroscopy in the 2–8 GHz frequency region. Two different gauche-gauche O-H···O hydrogen-bonded isomers were observed for the dimer of 2-adamantanol, while a single isomer was observed for the monomer and the monohydrate. The experimental rotational parameters were compared with molecular orbital calculations using density functional theory (B3LYP-D3(BJ), B2PLYP-D3(BJ), CAM-B3LYP-D3(BJ), ωB97XD), additionally providing energetic and electron density characterization. The shallow potential energy surface makes the dimer an interesting case study to benchmark dispersion-corrected computational methods and conformational search procedures.     

Enhanced Electromagnetic Wave Absorption Properties of Ultrathin MnO2 Nanosheet-Decorated Spherical Flower-Shaped Carbonyl Iron Powder

In this work, spherical flower-shaped composite carbonyl iron powder@MnO₂ (CIP@MnO₂) with CIP as the core and ultrathin MnO₂ nanosheets as the shell was successfully prepared by a simple redox reaction to improve oxidation resistance and electromagnetic wave absorption properties. The microwave-absorbing properties of CIP@MnO₂ composites with different filling ratios (mass fractions of 20%, 40%, and 60% after mixing with paraffin) were tested and analyzed. The experimental results show that compared with pure CIP, the CIP@MnO₂ composites have smaller minimum reflection loss and a wider effective absorption bandwidth than CIP (RL < −20 dB). The sample filled with 40 wt% has the best comprehensive performance, the minimum reflection loss is −63.87 dB at 6.32 GHz, and the effective absorption bandwidth (RL < −20 dB) reaches 7.28 GHz in the range of 5.92 GHz–9.28 GHz and 11.2 GHz–15.12 GHz, which covers most C and X bands. Such excellent microwave absorption performance of the spherical flower-like CIP@MnO₂ composites is attributed to the combined effect of multiple beneficial components and the electromagnetic attenuation ability generated by the special spherical flower-like structure. Furthermore, this spherical flower-like core–shell shape aids in the creation of discontinuous networks, which improve microwave incidence dispersion, polarize more interfacial charges, and allow electromagnetic wave absorption. In theory, this research could lead to a simple and efficient process for producing spherical flower-shaped CIP@MnO₂ composites with high absorption, a wide band, and oxidation resistance for a wide range of applications.     

Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride

Here we emphasise the importance of the dielectric environment on the electron transfer behavior in interfacial electrochemical systems. Through doping cobalt hexacyanide (Co(CN)₆^3–) into single microcrystals of sodium chloride (NaCl), for the first time, we obtained the direct electrochemical behavior of Co(CN)₆^3– which is hardly ever obtained in either aqueous or conventional nonaqueous solutions. DFT calculations elucidate that, as the Co(CN)₆^3– anions occupy the lattice units of NaCl₆^5– in the NaCl microcrystal, the redox energy barrier of Co(CN)₆^3–/4– is decreased dramatically due to the low dielectric constant of NaCl. Meanwhile, the low-spin Co(CN)₆^4– anions are stabilized in the lattices of the NaCl microcrystal. The results also show that the NaCl microcrystal is a potential solvent for solid-state electrochemistry at ambient temperature.     

MOFs-Derived Three-Phase Microspheres: Morphology Preservation and Electromagnetic Wave Absorption

Reasonable structural design and composition control are the dominant factors for tuning the electromagnetic absorbing properties of materials. In this paper, microspheres composed of NiO, Ni, and Co₃O₄ nanoparticles (NCMO) were successfully synthesized using a mild oxidation method. Benefiting from the multi-component composition and a unique microstructure, the RL_min of CNMO can reach −46.8 dB at 17 GHz, with an effective absorption bandwidth of 4.1 GHz (13.9–18 GHz). The absorbing properties and the absorbing mechanism analysis showed that the microsphere-structured NCMO composed of multi-component nanoparticles enhanced the interface polarization, thereby improving the absorption performance. This research provides a new avenue for MOF-derived oxide materials with excellent electromagnetic wave absorbing properties.     

A priori predictions of the rotational constants for protonated formaldehyde and protonated methanol

Protonated formaldehyde and protonated methanol are candidate interstellar molecules and models for classes of protonated oxygen compounds. Ab initio molecular orbital theory has been used to compute rotational constants to guide spectroscopic searches both in the laboratory and in space. The ab initio results are empirically corrected to account for systematic deficiencies in the theory and zero-point vibrational effects; they are expected to be accurate to approximately +/-2%. For H2COH+ the resultant constants are (in GHz) A = 194.3, B = 34.28, and C = 29.14; for H3COH2+ A = 103.7, B = 21.18, and C = 20.30.     

A priori predictions of the rotational constants for HC13N, HC15N, C5O

Ab initio molecular orbital theory is used to estimate the rotational constant for several carbon-chain molecules that are candidates for discovery in interstellar space. These estimated rotational constants can be used in laboratory or astronomical searches for the molecules. The rotational constant for HC13N is estimated to be 0.1073 +/- 0.0002 GHz and its dipole moment 5.4 D. The rotational constant for HC15N is estimated to be 0.0724 GHz, with a somewhat larger uncertainty. The rotational constant of C5O is estimated to be 1.360 +/- 2% GHz and its dipole moment 4.4. D.     

Formation of a C–C double bond from two aliphatic carbons. Multiple C–H activations in an iridium pincer complex

The search for novel, atom-economic methods for the formation of C–C bonds is of crucial importance in synthetic chemistry. Especially attractive are reactions where C–C bonds are formed through C–H activation, but the coupling of unactivated, alkane-type C_sp³–H bonds remains an unsolved challenge. Here, we report iridium-mediated intramolecular coupling reactions involving up to four unactivated C_sp³–H bonds to give carbon–carbon double bonds under the extrusion of dihydrogen. The reaction described herein is completely reversible and the direction can be controlled by altering the reaction conditions. With a hydrogen acceptor present a C–C double bond is formed, while reacting under dihydrogen pressure leads to the reverse process, with some of the steps representing net C_sp³–C_sp³ bond cleavage. Mechanistic investigations revealed a conceptually-novel overall reactivity pattern where insertion or deinsertion of an Ir carbene moiety, formed via double C–H activation, into an Ir–C bond is responsible for the key C–C bond formation and cleavage steps.     

The millimeter wave spectrum of iodoethyne,HCCI

The rotational spectrum of iodoethyne, HCCI, has been observed in the frequency range from 105 to 305 GHz. A sensitive spectrometer system employing source modulation, a harmonic generator millimeter wave source and a liquid helium cooled InSb-detector has been used. The rotational constants and nuclear quadrupole coupling parameters of HCCI have been obtained for the ground state and the first and second excited vibrational states of ν₄. The rotational spectrum of the 2ν₅ state has also been identified. The very weak spectrum shows unusual relative intensities which are interpreted by assuming a dipole moment change with ν₄ excitation of 0.07 D. The ground state dipole moment is then estimated to be 0.020(10) D.     

Microwave spectrum of bicyclo[2,2,1] hepta-2,5-dien-7-ol and spectroscopic evidence for an intramolecular (OH π) hydrogen bond

The microwave spectrum of bicyclo[2,2,1]hepta-2,5-dien-7-ol and of the deuteroxyl species have been recorded over 8–40 GHz. Rotational constants and centrifugal distortion constants were fitted to the measured rotational transitions for both species. The electric dipole components μm_a = 1.223(3) D, μm_b = 1.053(2) D and μm_total = 1.614(2) D were deduced from Stark splittings. Only a trans conformation of the OH group with respect to the hydrogen is compatible with the microwave data.Infrared spectra of bicyclo[2,2,1]hepta-2,5-dien-7-ol and the corresponding saturated compound have been recorded in the gas phase and in Ar matrix isolation. The difference of 77.4 cm⁻¹ in the O---H stretching frequencies between unsaturated and saturated compounds points towards a moderately strong intramolecular (OH π) hydrogen bond.     

Exploring the Dual Characteristics of CH3OH Adsorption to Metal Atomic Structures on Si (111)-7 × 7 Surface

Metal atoms were deposited on an Si (111)-7 × 7 surface, and they were adsorbed with alcohol gases (CH₃OH/C₂H₅OH/C₃H₇OH). Initially, C_nH_2n+1OH adsorption was simply used as an intermediate layer to prevent the chemical reaction between metal and Si atoms. Through scanning tunneling microscopy (STM) and a mass spectrometer, the C_nH_2n+1OH dissociation process is further derived as the construction of a surface quasi-potential with horizontal and vertical directions. With the help of three typical metal depositions, the surface characteristics of CH₃OH adsorption are more clearly presented in this paper. Adjusting the preheating temperature, the difference of thermal stability between CH₃O^– and H⁺ could be obviously derived in Au deposition. After a large amount of H⁺ was separated, the isolation characteristic of CH₃O^– was discussed in the case of Fe deposition. In the process of building a new metal-CH₃O^–-H⁺ model, the dual characteristics of CH₃OH were synthetically verified in Sn deposition. CH₃O^– adsorption is prone to influencing the interaction between the metal deposition and substrate surface in the vertical direction, while H⁺ adsorption determines the horizontal behavior of metal atoms. These investigations lead one to believe that, to a certain extent, the formation of regular metal atomic structures on the Si (111)-7 × 7-CH₃OH surface is promoted, especially according to the dual characteristics and adsorption models we explored.     

Optimization of β-1,4-Endoxylanase Production by an Aspergillus niger Strain Growing on Wheat Straw and Application in Xylooligosaccharides Production

Plant biomass constitutes the main source of renewable carbon on the planet. Its valorization has traditionally been focused on the use of cellulose, although hemicellulose is the second most abundant group of polysaccharides on Earth. The main enzymes involved in plant biomass degradation are glycosyl hydrolases, and filamentous fungi are good producers of these enzymes. In this study, a new strain of Aspergillus niger was used for hemicellulase production under solid-state fermentation using wheat straw as single-carbon source. Physicochemical parameters for the production of an endoxylanase were optimized by using a One-Factor-at-a-Time (OFAT) approach and response surface methodology (RSM). Maximum xylanase yield after RSM optimization was increased 3-fold, and 1.41- fold purification was achieved after ultrafiltration and ion-exchange chromatography, with about 6.2% yield. The highest activity of the purified xylanase was observed at 50 °C and pH 6. The enzyme displayed high thermal and pH stability, with more than 90% residual activity between pH 3.0–9.0 and between 30–40 °C, after 24 h of incubation, with half-lives of 30 min at 50 and 60 °C. The enzyme was mostly active against wheat arabinoxylan, and its kinetic parameters were analyzed (K_m = 26.06 mg·mL⁻¹ and V_max = 5.647 U·mg⁻¹). Wheat straw xylan hydrolysis with the purified β-1,4 endoxylanase showed that it was able to release xylooligosaccharides, making it suitable for different applications in food technology.     

Synthesis and spectroscopic properties of (N/O) mono- and dispirocyclotriphosphazene derivatives with benzyl pendant arms: study of biological activity

The Cl replacement reactions of hexachlorocyclotriphosphazene (trimer; N ₃ P ₃ Cl ₆ ) with sodium (N-benzyl)- aminopropanoxides (1 and 2) produced monospiro- (3 and 4), cis-, and trans-dispirocyclotriphosphazenes (13–16). The monospiro tetrakis-aminocyclotriphosphazenes (5–12) were obtained by the Cl substitutions of 3 and 4 with different secondary amines. The cis- (13 and 14) and trans-dispirophosphazenes (15 and 16) possessed 2 chiral P centers, and they were able to present meso and racemic forms, respectively. Moreover, the structures of compounds 5 and 14 were designated using X-ray data. The absolute configuration of compound 14 was found as SR in the solid state. Analytical and spectroscopic data of the phosphazenes were consistent with their suggested structures. Antimicrobial activities of the benzyl-pendant-armed cyclotriphosphazenes were scrutinized against G(+) and G(−) bacteria and yeast strains. The bacterium most affected by the synthesized compounds was Pseudomonas aeruginosa . Minimum inhibitory concentrations and minimal bacterial concentrations were in the range of 125–500 μM. Interactions between the phosphazenes (3–12 and 15) and plasmid DNA were studied with agarose gel electrophoresis. The phosphazene- DNA interaction studies of the cyclotriphosphazenes revealed that phosphazenes 3, 4, and 15 had a substantial effect on supercoiled DNA by cleavage of the double helix.