INS,IR, RAMAN, 1H NMR and DFT investigations on dynamical properties of l-asparagine

Results of inelastic neutron scattering (INS), infra-red (IR), Raman and ¹H NMR spectroscopy used for investigations on the l-asparagine dynamics are reported. The crystallographic structure and experimental vibrational spectra are compared with those calculated by the DFT methods applied to the solid state. Very good conformity of the experimental and theoretical structures has been found. The NH₃⁺ torsional vibration mode is observed in the INS spectra at 494 cm⁻¹, while the bands assigned to the vibrations of the strong NH⋯O hydrogen bonds are observed at 2849, 2650, and 2480 cm⁻¹ in the IR spectrum. A ¹H NMR investigation has been carried out at 26.75 MHz in the temperature range 150–300 K. For l-asparagine the activation energy needed for the NH₃⁺ group reorientation is equal 5.6 kcal/mol.     

Cation-π Interactions between a Noble Metal and a Polyfunctional Aromatic Ligand: Ag+(benzylamine)

The structure of an isolated Ag⁺(benzylamine) complex is investigated by infrared multiple photon dissociation (IRMPD) spectroscopy complemented with quantum chemical calculations of candidate geometries and their vibrational spectra, aiming to ascertain the role of competing cation-N and cation-π interactions potentially offered by the polyfunctional ligand. The IRMPD spectrum has been recorded in the 800–1800 cm⁻¹ fingerprint range using the IR free electron laser beamline coupled with an FT-ICR mass spectrometer at the Centre Laser Infrarouge d'Orsay (CLIO). The resulting IRMPD pattern points toward a chelate coordination (N-Ag⁺-π) involving both the amino nitrogen atom and the aromatic π-system of the phenyl ring. The gas-phase reactivity of Ag⁺(benzylamine) with a neutral molecular ligand (L) possessing either an amino/aza functionality or an aryl group confirms N- and π-binding affinity and suggests an augmented silver coordination in the product adduct ion .     

Vibrational spectroscopy of lapachol, α- and β-lapachone: Theoretical and experimental elucidation of the Raman and infrared spectra

Raman and infrared spectroscopy were applied for the vibrational characterization of lapachol and its pyran derivatives, α-lapachone and β-lapachone. Experimental spectra of solid state samples were acquired between 4000 and 100 cm⁻¹ in Raman experiments, and between 4000 and 600 cm⁻¹ (mid-infrared) and 600–100 cm⁻¹ (far-infrared) with FTIR spectroscopy, respectively. Full structure optimization and theoretical vibrational wavenumbers were calculated at the B3LYP/6-31 + + G(d,p) level. Detailed assignments of vibrational modes in an experimental and theoretical spectra were based on potential energy distribution analyses, using Veda 4.1 software. Clear differentiation between the three compounds was verified in the region between 1725 and 1525 cm⁻¹, in which the ν(CO) and ν(CC) modes of the quinone moiety were assigned.     

Two Coordination Modes of CO in Zeolites: A Temperature-Dependent Equilibrium

CO interacts with exchangeable cations M⁺ (gray spheres in the picture) of zeolites to form M⁺⋅⋅⋅CO and M⁺⋅⋅⋅OC species (C: black; O: white) which are in a temperature-dependent equilibrium. For Na-ZSM-5 (M⁺=Na⁺) the difference in interaction energy amounts to 3.8 kJ mol⁻¹, as determined by means of variable-temperature FT-IR spectroscopy.     

Alkali metal intercalated titanate nanotubes: A vibrational spectroscopy study

Alkali metal (Li⁺, Na⁺, K⁺) intercalated titanate nanotubes have been studied by vibrational spectroscopy (Raman and FT-infrared), X-ray diffraction, and electron microscopy. The vibrational spectroscopic data shown that the most affected vibrational mode is that related to Ti-O bond whose oxygen is not shared among the TiO₆ units of the framework structure. A correlation between vibrational frequency shifts and intercalated metal was found, thus showing that vibrational spectroscopy is very useful for probing metal intercalated titanate nanotubes. Our results provide good evidences that the structure of titanate layers in titanate nanotube, a subject of long debate in the literature, is similar to trititanates (like Na₂Ti₃O₇).     

Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O⁻…H⁺…⁻OCO) features a single local minima, with the proton localized on the O⁻ group (OH…⁻OCO). However, the structure with the proton localized on the ⁻OCO group (O⁻…HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…⁻OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…⁻OCO isomer decarboxylate without barrier, while the radicals produced from the O⁻…HOCO isomer are stable.     

Magnetic Chirality Transitions of D- and L-Alanine

A chiral spin state of (N⁺H) in D- and L-alanine was established by monitoring the temperature dependence of dc-magnetic susceptibility (dc: direct current) under the external magnetic field of 1 T. An intrinsic spin chirality of electrons in the atomic magnetic dipole moment of (N⁺H) was also supported by polarized Raman spectroscopy. Magnetic chirality was associated with a strongly correlated electron system that was related to spin rigidity. Raman vibrational spectra were unrelated to structural chirality but could reflect spin chirality due to the reversal of motion breaking. The spin transition of (N⁺H) occured at 270 K without bond breaking but was assisted by an intermediate hydrogen bond elongation, splitting and reformation with NH₃⁺ torsion. The energy difference of spin chirality transitions between D- and L-alanine was around 10⁻⁴-10⁻⁵ eV·molecule⁻¹.     

Vibrational vave-packet dynamics in CV670 investigated by broadband femtosecond TR-CARS spectroscopy

Broadband femtosecond time-resolved coherent anti-Stokes Raman scattering ((TR-CARS)) is utilized to investigate the wave-packet dynamics of Cresyl Violet (CV670) dye molecules in ethanol solvent at room temperature. An interesting behavior of wave-packet dynamics phenomena is observed and discussed for the first time, and several unknown Raman vibrational modes with frequency differences of 32 cm⁻¹, 38 cm⁻¹, 45 cm⁻¹, 50 cm⁻¹, 55 cm⁻¹, 65 cm⁻¹, 80 cm⁻¹, 95 cm⁻¹ and 101 cm⁻¹ are excited and obtained at the same time. This work makes possible high efficiency in the structure investigation as well as dynamics of intra-molecular processes by broadband femtosecond (TR-CARS) spectroscopy with fast Fourier transformation (FFT) analysis means.     

Spectroscopic studies of the 1:1 complex of piperidine-4-carboxylic acid (isonipecotic acid) with 2,6-dichloro-4-nitrophenol

The 1:1 complex of piperidine-4-carboxylic acid (isonipecotic acid, P4C) with 2,6-dichloro-4-nitrophenol (DCNP), has been investigated by single-crystal X-ray analysis, Raman and FTIR spectroscopy and theoretical calculations. The hydrogen-bonded-ion-pair complex is observed in the crystalline state with the O⋯H⋯OOC hydrogen bond of 2.453(16) Å. FTIR spectrum shows a broad absorption in the 1600–400 cm⁻¹ region characteristic of very short OHO hydrogen bond, broken by the Evans holes. The complexes are joined through NH⋯O into a H-bonding network. The NH⋯O mode appears as a broad band in the range of 3100–2000 cm⁻¹. In the structure optimized at the B3LYP/6–311 + +G(d,p) level of theory the proton is transferred from DCNP to P4C, and molecules are joined through the O⋯HOOC hydrogen bond of 2.640 Å. The experimental and theoretical infrared spectra are discussed. Detail interpretation of the vibrational spectra has been carried out with the use of computed Potential Energy Distribution (PED).     

Trihydroxycarbenium Hexafluorometalates: Salts of Protonated Carbonic Acid

Stabilization by salt formation : carbonic acid, which is not available as a pure substance, was isolated in the form of its trihydroxycarbenium salts, C(OH)₃⁺ MF₆⁻ (M=As, Sb), from the reaction of carbonic acid bis(trimethylsilyl) ester in the superacids HF/MF₅. The structure of the cation is shown in the picture. The ion was also characterized by vibrational spectroscopic studies.     

Structure and Fluxionality of B13+ Probed by Infrared Photodissociation Spectroscopy

We use cryogenic ion vibrational spectroscopy to characterize the structure and fluxionality of the magic number boron cluster B₁₃⁺. The infrared photodissociation (IRPD) spectrum of the D₂‐tagged all‐¹¹B isotopologue of B₁₃⁺ is reported in the spectral range from 435 to 1790 cm⁻¹ and unambiguously assigned to a planar boron double wheel structure based on a comparison to simulated IR spectra of low energy isomers from density‐functional‐theory (DFT) computations. Born–Oppenheimer DFT molecular dynamics simulations show that B₁₃⁺ exhibits internal quasi‐rotation already at 100 K. Vibrational spectra derived from these simulations allow extracting the first spectroscopic evidence from the IRPD spectrum for the exceptional fluxionality of B₁₃⁺.     

Hybrid graphene oxide/DAB-Am-16 dendrimer: Preparation,characterization chemical reactivity and their electrocatalytic detection of l-Dopamine

Graphene oxide (GO) was chemically modified with a poly(propylene)imine Generation 3.0 dendrimer (DAB-Am-16). The characterization, structure and properties of hybrid graphene oxide/DAB-Am-16 dendrimer was studied by Raman spectroscopy, Fourier-Transforming Infrared Spectroscopy (FT-IR), X-Ray Photoelectron Spectroscopic (XPS), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis. After functionalized the hybrid material (GOD) can interact with copper and subsequently with hexacyanoferrate (III) ions (GODHCu). The GODHCu incorporated into a graphite paste electrode (20% w/w) was applied to an electrocatalytic detection of neurotransmitter l-dopamine using differential pulse voltammetry. The analytical curve showed a linear response in the concentration range from 1.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol L⁻¹ with a corresponding equation Y(A) = 1.706 × 10⁻⁵ + 0.862 [l-dopamine] and a correlation coefficient r² = 0.998. The detection limit was 6.36 × 10⁻⁷ mol L⁻¹ with a relative standard deviation of ±4% (n = 3) and an amperometric sensitivity of 0.862 A/mol L⁻¹.     

Hidden Isolated OH at the Charged Hydrophobic Interface Revealed by Two-Dimensional Heterodyne-Detected VSFG Spectroscopy

Water around hydrophobic groups mediates hydrophobic interactions that play key roles in many chemical and biological processes. Thus, the molecular-level elucidation of the properties of water in the vicinity of hydrophobic groups is important. We report on the structure and dynamics of water at two oppositely charged hydrophobic ion/water interfaces, that is, the tetraphenylborate-ion (TPB⁻)/water and tetraphenylarsonium-ion (TPA⁺)/water interfaces, which are clarified by two-dimensional heterodyne-detected vibrational sum-frequency generation (2D HD-VSFG) spectroscopy. The obtained 2D HD-VSFG spectra of the anionic TPB⁻ interface reveal the existence of distinct π-hydrogen bonded OH groups in addition to the usual hydrogen-bonded OH groups, which are hidden in the steady-state spectrum. In contrast, 2D HD-VSFG spectra of the cationic TPA⁺ interface only show the presence of usual hydrogen-bonded OH groups. The present study demonstrates that the sign of the interfacial charge governs the structure and dynamics of water molecules that face the hydrophobic region.     

Secondary interactions in the iso­morphous compounds 2,6‐bis­(chloro­methyl)­pyridinium chloride and 2,6‐bis­(bromo­methyl)­pyridinium bromide

The title compounds, C₇H₈Cl₂N⁺·Cl⁻ and C₇H₈Br₂N⁺·Br⁻, are isomorphous. In the crystal packing, layers parallel to the ac plane are formed by a classical N⁺—H⋯X⁻ hydrogen bond (X = halogen) and two X⋯X contacts. A third X⋯X contact links the layers, and a fourth, which is however very long, completes a ladder‐like motif of halogen atoms. Hydro­gen bonds of the form C—H⋯X play at best a subordinate role in the packing.     

The confinement and anion type effect on the physicochemical properties of ionic liquid/halloysite nanoclay ionogels

This work is the first attempt to study the physicochemical properties of ionogels - quasi-solid hybrid materials formed by ionic liquids (ILs) − 1-butyl-3-methylimidazolium (BMIm⁺) salts with dicyanamide- (DCA⁻), bis(trifluoromethylsulfonyl)imide- (TFSI⁻), and trifluoromethanesulfonate- (Otf⁻) anions - and halloysite, a powdered clay filler with nanotube particles (at the IL:Hal molar ratio of 2:1) in order to find possible new applications of ionic liquids and industrial minerals. The electron microscopy, TG, and DSC analysis, FTIR spectroscopy, X-ray diffraction analysis, conductometry and cyclic voltammetry methods are used to investigate the anion effect on the IL interaction with halloysite. It has, for the first time, been found that the distinguishing feature of halloysite interaction with an IL determining the structural changes in the clay mineral and electrochemical characteristics of the ionogels is partial dehydration of the clay and absorption of the released water by the ionic liquid. It is shown that the halloysite dehydration effect depends on the IL hydrophilicity determined by the anion type, corresponds to the series: BMImDCA > BMImOtf > BMImTFSI. The electrochemical and thermal behaviour of ILs confined within a halloysite matrix differs from that of bulk ILs and is controlled by the anion type. Temperature dependences of the structural resistance of the halloysite filler are radically different for the ILs with high and low hydrophilicity. The effects resulting from the formation of halloysite-based ionogels can be of interest to those who develop quasi-solid ionic conductors that can work within a wide temperature range.     

Investigation of sport supplements quality by Raman spectroscopy and principal component analysis

In this work, sport supplements were investigated by Raman spectroscopy. Samples were obtained from health foods shops, gyms and sports centers covering a wide range of available supplement powders. A systematic comparison of Raman spectra of the analyzed supplements allowed identifying the supplement type through the characteristic vibrational modes of carbohydrates and proteins. The protein supplements were identified by Raman bands at 1650, 1250 and 1004 cm⁻¹, while the spectral range between 1200 and 800 cm⁻¹ was useful to identify the carbohydrate supplements. Due to the diversity in composition of sport supplements, a chemometric tool such as principal component analysis (PCA) was employed to assist in the interpretation of Raman spectra, allowing also the identification of compounds present in sport supplements. Especially, the Raman scattering of aromatic and aliphatic amino acids residues contributes to the existence of bands characteristic for the different types of proteins. This kind of information is very important for the quality control of these products, for detecting the presence of fraud or a sample composition in disagreement with the label, thus ensuring the provenance of the supplements.     

Dissecting Noncovalent Interactions in Carboxyl-Functionalized Ionic Liquids Exhibiting Double and Single Hydrogens Bonds Between Ions of Like Charge

We show that the carboxyl-functionalized ionic liquid 1-(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC-CH₂-py][NTf₂] exhibits three types of hydrogen bonding: the expected single hydrogen bonds between cation and anion, and, surprisingly, single and double hydrogen bonds between the cations, despite the repulsive Coulomb forces between the ions of like charge. Combining X-ray crystallography, differential scanning calorimetry, IR spectroscopy, thermodynamic methods and DFT calculations allows the analysis and characterization of all types of hydrogen bonding present in the solid, liquid and gaseous states of the ionic liquid (IL). We find doubly hydrogen bonded cationic dimers (c⁺=c⁺) in the crystalline phase. With increasing temperature, this binding motif opens in the liquid and is replaced by (c⁺−c⁺−a⁻ species, with a remaining single cationic hydrogen bond and an additional hydrogen bond between cation and anion. We provide clear evidence that the IL evaporates as hydrogen-bonded ion pairs (c⁺−a⁻) into the gas phase. The measured transition enthalpies allow the noncovalent interactions to be dissected and the hydrogen bond strength between ions of like charge to be determined.     

Darstellung der Halogennitrilium-Salze XCNH+MF6− (X = Cl,Br, I; M = As,Sb) und der Trifluoracetonitrilium-Salze CF3CNH+MF6−

Preparation of the Halogenonitrilium Salts XCNH⁺MF₆⁻ (X = CI, Br, I; M = As, Sb) and the Trifluoroacetonitrilium Salts CF₃CNH⁺MF₆⁻ The halogenonitrilium salts XCNH⁺MF₆⁻ (X = CI, Br, I; M = As, Sb) are synthesized by protonation of cyanogen halides in the superacide system HF/MF₅ at low temperature. The synthesis of trifluoroacetonitrilium salts CF₃CNH⁺MF₆⁻ (M = As, Sb) is proceeded analogous with trifluoroacetonitrile. All salts are characterized by vibrational and NMR spectroscopy.     

Berberine formate–succinic acid (1/1)

The title compound [systematic name: 9,10‐di­methoxy‐2,3‐methyl­ene­dioxy‐5,6‐di­hydro­dibenzo­[a,g]­quinolizinium form­ate–succinic acid (1/1)], C₂₀H₁₈NO₄⁺·CHO₂⁻·C₄H₆O₄, con­tains centrosymmetric pairs of almost planar berberine cations, and hydrogen‐bonded (C₄H₆O₄⋯HCOO⁻)₂ rings of succinic acid with formate anions, bonded by O—H⋯O hydrogen bonds with O⋯O distances of 2.4886 (15) and 2.5652 (16) Å. Pairs of cations and mol­ecules of succinic acid are connected by non‐conventional weak C—H⋯O hydrogen bonds, with C⋯O distances of 3.082 (2) and 3.178 (2) Å.