Vibrationally Resolved Absorption, Fluorescence, and Preresonance Raman Spectroscopy of Isolated Pyronin Y Cation at 5 K.

Exploring how charge-changing affects the photoluminescence of small organic dyes presents challenges. Here, helium tagging photodissociation (PD) action spectroscopy in the gas phase and dispersed laser-induced fluorescence (DF) spectroscopy in the solid Ne matrix are used to compare the intrinsic photophysical properties of pyronin Y cation [PY]+ and its one electron-reduced neutral radical [PY]• at 5 K. Whereas the cation shows efficient visible photoluminescence, no emission from the neutral, in line with theoretical predictions, was detected. B3LYP/aug-cc-pVDZ calculations based on the TD-DFT/FCHT method allow for unambiguous assignment of recorded vibrationally resolved absorption and emission spectra. Surprisingly, our experimental sensitivity was high enough to also observe electronic preresonance Raman (ePR-Raman) spectra of [PY]+, with a significant efficiency factor (EF). These characteristics of the [PY]•/[PY]+ pair suggest that appropriately functionalized derivatives may open new perspectives in the area of in vivo bioimagining microscopy and find applications in various sophisticated stimulated-Raman spectroscopies.

Hydrogen-Atom-Assisted Uphill Isomerization of N-Methylformamide in Darkness.

N-Methylformamide, HC(O)NH(CH3), is the smallest amide detected in the interstellar medium that can exist as cis and trans isomers. We performed reactions of H atoms with trans-NMF in solid para-hydrogen at 3.3 K and found that the cis-NMF isomer, which has higher energy, increased continuously in darkness, demonstrating a previously overlooked and seemingly unlikely isomerization of prebiotic molecules through H-atom tunneling reactions in the absence of light. Infrared spectra of radical intermediates trans-•C(O)NH(CH3) and trans-HC(O)NH(•CH2) were identified. Further H addition and H abstraction enhanced the formation of CH3NCO, HNCO, and CH2NH in the H-rich experiments. These results indicate that, unlike the dual cycle of H-abstraction and H-addition channels chemically linking formamide and HNCO, the H addition to CH3NCO produced only cis-radicals that led to cis-NMF. Furthermore, H-atom-induced fragmentation by breaking the C-C bond provides links between NMF and HCNO/CH2NH. These endothermic isomerization/decomposition reactions become possible through the coupling with H + H → H2.

Triggering near-infrared luminescence of vanadyl phthalocyanine by charging.

Probing electrofluorochromism (EFC) at the molecular level remains challenging. Here we study the strongly charge state-dependent photoluminescence of vanadyl phthalocyanine. We report vibrationally resolved absorption and laser-induced fluorescence (LIF) spectra of samples comprising both the mass-selected neutral molecule (VOPc⋅, a stable radical) and its cation produced upon electron ionization (EI) isolated in 5 K neon matrices. Ionization of the essentially non-emissive VOPc⋅ forms a high-spin diradical cation (VOPc+.. ) which shows profound photoluminescence (PL) in the NIR range. This unique phenomenon is potentially of interest for NIR-emitting electro-optic devices.

Vibrationally Resolved Absorption and Luminescence Spectra of Mass-Selected Free-Base and Zinc Phthalocyanine Radical Cations Isolated in Solid Ne.

We report the first vibrationally well-resolved absorption and laser-induced fluorescence spectra of the radical cations of free-base phthalocyanine (H2Pc+) and zinc phthalocyanine (ZnPc+) isolated in 5 K neon matrices and compare them to the spectral properties of the corresponding neutrals. The samples were generated by low-energy deposition of the mass-selected ions. The spectra are also discussed in terms of time-dependent density functional theory calculations and compared with recently reported scanning tunneling microscopy-induced single-molecule luminescence of the same species adsorbed on NaCl-covered Au(111) or Ag(111) single crystal supports.

Photoactivated Refractive Index Anisotropy in Fluorescent Thiophene Derivatives.

The optical control of anisotropy in materials is highly advantageous for many technological applications, including the real-time modulation of another light signal in photonic switches and sensors. Here, we introduce three thiophene derivatives with a donor-acceptor structure, which feature different positions of an electron-acceptor nitrile group, and both photoalignment and luminescence properties. Quantum chemical calculations highlight the presence of trans-forms stable at room temperature and metastable cis-isomers. Besides photoluminescence peaked at 440-460 nm and 0.4 ns lifetime, the three nonlinear optical chromophores exhibit photoinduced anisotropy of the refractive index closely depending on the specific molecular structure, with higher values of birefringence at lower driving signal being obtained for ortho substitution of the nitrile group. All-optical modulation of an external light beam at rates of hundreds of hertz is demonstrated in the fluorescent systems. This finding opens an interesting route to multispectral photonic switches embedded in the active layers of light-emitting devices.

Infrared Spectra of (Z)- and (E)-•C2H3C(CH3)I Radicals Produced upon Photodissociation of (Z)- and (E)-(CH2I)HC═C(CH3)I in Solid para-Hydrogen.

Ozonolysis of isoprene to produce Criegee intermediates such as methyl vinyl ketone oxide (MVKO), C2H3C(CH3)OO, is an important process in atmospheric chemistry. MVKO was recently produced and identified in laboratories after photolysis of a gaseous mixture of 1,3-diiodo-but-2-ene, (CH2I)HC═C(CH3)I, and O2, but the mechanism of its formation remains unexplored. We synthesized pure (Z)- and (E)-1,3-diiodo-but-2-ene and measured their distinct IR spectra. Upon irradiation at 280 nm of (Z)- and (E)-1,3-diiodo-but-2-ene in solid p-H2 at 3.3 K, the fission of the terminal C-I bond yields (Z)- and (E)-3-iodo-but-2-en-1-yl [•C2H3C(CH3)I] radicals, respectively. These radicals were characterized with infrared absorption lines at 2962.4, 1423.8, 1265.3, 1120.9/1127.0, 921.4/922.3, and 792.5/791.7 cm-1, and 16 additional weaker lines for (Z)-•C2H3C(CH3)I and 1405.2, 1208.2, 1106.0/1103.9, 934.2/933.4, and 785.1/784.9 cm-1 and five additional weaker ones for (E)-•C2H3C(CH3)I. The assignments were derived according to behavior on secondary photolysis and comparison of the vibrational wavenumbers and the IR intensities of observed lines with those calculated with the B2PLYP-D3/aug-cc-pVTZ-pp method. These observations confirmed that only the terminal I atom, not the central one, was photodissociated at 280 nm and, in solid p-H2, the excess energy after photodissociation induced no change in conformation. These new spectra of •C2H3C(CH3)I radicals can provide valuable information for the understanding of the mechanism of formation of Criegee intermediate MVKO from the source reaction of photolysis of (CH2I)HC═C(CH3)I in O2 in the laboratory.

Hydrogen abstraction in astrochemistry: formation of ˙CH2CONH2 in the reaction of H atom with acetamide (CH3CONH2) and photolysis of ˙CH2CONH2 to form ketene (CH2CO) in solid para-hydrogen.

Acetamide (CH3CONH2) is the largest molecule containing an amide bond that has been detected in an interstellar medium; it is considered to be a precursor for complex organic molecules (COM). We utilized the advantages of a para-hydrogen (p-H2) quantum-solid matrix host to perform efficient reactions of hydrogen atoms with CH3CONH2. The H-abstraction reaction from the methyl group of CH3CONH2 to produce the 2-amino-2-oxoethyl radical, ˙CH2CONH2, was observed as the sole reaction channel in solid p-H2 at 3.3 K, consistent with theoretical predictions that this reaction has the smallest barrier among all possible channels. Our results show that the amide bond of acetamide is unaffected by hydrogen exposure, but the hydrogen abstraction activates this molecule to react with other species on its methyl site to extend its size or to include other functional groups as a first step to form COM under prebiotic or abiotic conditions. This previously neglected path should be considered in the astrochemical modeling. The photolysis of ˙CH2CONH2 at wavelengths 380-450 nm produces ketene; this step might provide a plausible mechanism to explain the anti-correlated abundance of ketene and acetamide in some astronomical observations.

Hydrogen-atom tunneling reactions with methyl formate in solid para-hydrogen: Infrared spectra of the methoxy carbonyl [•C(O)OCH3] and formyloxy methyl [HC(O)OCH2•] radicals.

We investigated the reaction of methyl formate, HC(O)OCH3, with hydrogen atoms in solid para-hydrogen (p-H2) at 1.74 and 3.3 K with infrared absorption spectroscopy. Hydrogen atoms were produced either upon direct photolysis of HC(O)OCH3 at 193 nm or upon irradiation of Cl2, codeposited with HC(O)OCH3 in p-H2, with light at 365 nm to produce Cl atoms that react with the p-H2 host via the reaction Cl + H2 (ν = 1) → HCl + H induced by subsequent IR irradiation of the p-H2 matrix. We assigned lines at 1785.2, 1170.6, 1104.6, and 879.4/880.5 cm-1 and five additional weak lines to the methoxy carbonyl radical, •C(O)OCH3, and three weak lines at 1751.3, 1152.9, and 994.4/996.8 cm-1 to the formyloxy methyl radical, HC(O)OCH2•, according to the consideration of possible reactions, correlated variations in intensities after each experimental step, and comparison of observed vibrational wavenumbers and IR intensities with values predicted with the B3LYP/aug-cc-pVTZ method. Unlike most reported H-atom diffusion tunneling reactions, the reaction H + HC(O)OCH3 in solid p-H2 at 3.3 K was found to diminish rapidly after IR irradiation, but, similar to reactions of H + N2O and H + HC(O)OH, this reaction was reinitiated when the matrix temperature was decreased from 4.0 K to 1.5 K. We confirmed that the method used to generate the mobile H atoms does not affect the subsequent chemistry. A possible reaction mechanism and the role of this reaction in dark interstellar clouds are discussed.

Hydrogen Abstraction/Addition Tunneling Reactions Elucidate the Interstellar H2NCHO/HNCO Ratio and H2 Formation.

Formamide (H2NCHO) is the smallest molecule possessing the biologically important amide bond. Recent interstellar observations have shown a strong correlation between the abundance of formamide and isocyanic acid (HNCO), indicating that they are likely to be chemically related, but no experiment or theory explains this correlation satisfactorily. We performed H + H2NCHO reactions in a para-hydrogen quantum-solid matrix host and identified production of H2NCO and HNCO from hydrogen-abstraction reactions. We identified also D2NCO, DNCO, HDNCO, and HDNCHO from the reaction H + D2NCHO, indicating the presence of hydrogen-addition reactions of DNCO and HDNCO. From the observed temporal profiles of H2NCHO, H2NCO, HNCO, and their deuterium isotopologues, we showed that a dual-cycle consisting of hydrogen abstraction and hydrogen addition can satisfactorily explain the quasi-equilibrium between H2NCHO and HNCO and explain other previous experimental results. Furthermore, this mechanism also indicates that the catalytic formation of H2 from H atoms might occur in interstellar ice grains.

Low-Molecular Push-Pull Pyrazoline Derivatives: Solvatochromic Effect and Theoretical Insights into Dye-based Molecular Engineering.

Intermolecular interactions between dyes and solvents are essential in understanding a number of phenomena. In this contribution, we focused on similarities and differences between two molecules belonging to the same pyrazoline derivatives group: the small and rigid- 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1 H-pyrazole (DCNP) molecule and the quite long and flexible one of (4-(2-(1-phenyl-4,5-dihydro-1 H-pyrazol-3-yl)vinyl)benzylidene) malononitrile (PY-PhdiCN). We experimentally show and use theoretical calculations to prove that extension of π-connector significantly changes the electrostatic potential distribution, which results in delocalization of negative charge along the whole donor group and increases potential surface of interaction with solvent molecules giving large spectral shifts. We also show that pyrazoline derivatives are very effective and sensitive solvent indicators with long-time stability.

Photodissociation of CF2ICF2I in solid para-hydrogen: infrared spectra of anti- and gauche-˙C2F4I radicals.

The photolysis of 1,2-diiodotetrafluoroethane (CF2ICF2I) has served as a prototypical system in ultrafast reaction dynamics. Even though the intermediates, anti- and gauche-iodotetrafluoroethyl (˙C2F4I) radicals, have been characterized with electron diffraction and X-ray diffraction, their infrared spectra are unreported. We report the formation and infrared identification of these radical intermediates upon ultraviolet photodissociation of CF2ICF2I in solid para-hydrogen (p-H2) at 3.3 K. Lines at 1364.9/1358.5, 1283.2, 1177.1, 1162.2, 1126.8, 837.3, 658.0, 574.2, and 555.2 cm-1 are assigned to anti-˙C2F4I, and lines at 1325.9, 1259.7, 1143.4, 1063.4, 921.0, and 765.3 cm-1 to gauche-˙C2F4I. A secondary photodissociation leading to C2F4 was also observed. The assignments were derived according to behavior on secondary photolysis, comparison of the vibrational wavenumbers and the IR intensities of the observed lines with values predicted with the B3PW91/aug-cc-pVTZ-pp method. This spectral identification provides valuable information for future direct spectral probes of these important intermediates.

All-Optical Switching and Two-States Light-Controlled Coherent-Incoherent Random Lasing in a Thiophene-Based Donor-Acceptor System.

We describe herein the synthesis and characterization of a thiophene-based donor-acceptor system, namely (E)-2-(4-nitrostyryl)-5-phenylthiophene (Th-pNO2 ), which was prepared under Horner-Wadsworth-Emmons conditions. The UV/Vis absorption bands, including the intramolecular charge transfer (ICT) band, were fully assigned using DFT and TD-DFT computations. The results of both efficient third-order nonlinear optical properties and light-amplification phenomena are presented. Investigations of photoinduced birefringence (PIB) in optical Kerr effect (OKE) experiments showed a great potential for this particular compound as an efficient, fully reversible, and fast optical switch. Time constants for the observed trans-cis-trans molecular transitions are in the range of microseconds and give a competitive experimental result for the well-known and exploited azobenzene derivatives. Random lasing (RL) investigations confirmed that this organic system is potentially useful to achieve strong light enhancement, observed as a multimode lasing action. Both RL and OKE measurements indicate that this material is a representative of thiophene derivatives, which can be utilized to fabricate fast all-optical switches or random lasers (light amplifiers).

Structural and spectroscopic characterization of DMF complexes with nitrogen, carbon monoxide, ammonia and water. Infrared matrix isolation and theoretical studies [corrected].

An infrared spectroscopic and MP2/6-311++G(2d,2p) study of the complexes between N,N-dimethylformamide (DMF) and nitrogen, carbon monoxide, water, ammonia trapped in solid argon matrices is reported [corrected]. The 1:1 molecular complexes have been identified in the DMF/B/Ar matrices (B=N2, CO, H2O, NH3); their structures were determined by comparison of the spectra with the results of calculations. The analysis of the experimental and theoretical data indicate that the DMF-N2, CO complexes present in the matrices are stabilized by (C=)O⋯N and (C=)O⋯C van der Waals interactions. In turn, in the DMF-H2O, NH3 complexes the (C=)O⋯H(OH) and (C=)O⋯H(NH2) hydrogen bonding is present in which the carbonyl group of DMF acts as a proton acceptor. In all systems studied the C-H⋯X (X=N, C, O) bonding is a second intermolecular force stabilizing the planar complexes. Some spectral features indicate that for DMF-H2O, DMF-NH3 systems the nonplanar structures with the C=O⋯H interaction are also present. The study demonstrated the strong sensitivity of the CH stretching wavenumber to an involvement of the C-H and/or C=O groups of DMF in an intermolecular interaction.

Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen.

The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C3v to Cs provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH2DO in a matrix of p-H2 has been recorded. This species was prepared by irradiating a p-H2 matrix containing deuterated d1-nitritomethane (CH2DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH2DO reacts with H2 with a rate coefficient (3.5 ± 1.0) × 10-3 s-1. Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + Cs-CH2DOH, which was demonstrated by an additional experiment on irradiation of a CH2DOH/Cl2/p-H2 matrix with ultraviolet and IR light to induce the H + CH2DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm-1, the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d2-methoxy radical (CHD2O) was obtained upon irradiation of d2-nitritomethane (CHD2ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD2O reacts with H2 with a rate coefficient (6.0 ± 1.4) × 10-3 s-1; CD2OH was produced as a major product because the barrier for the formation of CHDOH from H + CHD2OH is greater by ∼400 cm-1. Rate coefficients of the decays of CH3O, CH2DO, CHD2O, and CD3O and their corresponding potential energy surfaces are compared.

Reaction of H + HONO in solid para-hydrogen: infrared spectrum of ˙ONH(OH).

Hydrogenation reactions in the N/O chemical network are important for an understanding of the mechanism of formation of organic molecules in dark interstellar clouds, but many reactions remain unknown. We present the results of the reaction H + HONO in solid para-hydrogen (p-H2) at 3.3 K investigated with infrared spectra. Two methods that produced hydrogen atoms were the irradiation of HONO molecules in p-H2 at 365 nm to produce OH radicals that reacted readily with nearby H2 to produce mobile H atoms, and irradiation of Cl2 molecules (co-deposited with HONO) in p-H2 at 405 nm to produce Cl atoms that reacted, upon IR irradiation of the p-H2 matrix, readily with nearby H2 to produce mobile H atoms. In both experiments, we assigned IR lines at 3549.6 (ν1), 1465.0 (ν3), 1372.2 (ν4), 898.5/895.6 (ν6), and 630.9 (ν7) cm-1 to hydroxy(oxido)-λ5-azanyl radical [˙ONH(OH)], the primary product of HONO hydrogenation. Two weak lines at 3603.4 and 991.0 cm-1 are tentatively assigned to the dihydroxy-λ5-azanyl radical, ˙N(OH)2. The assignments were derived according to the consideration of possible reactions and comparison of observed vibrational wavenumbers and their IR intensities with values predicted quantum-chemically with the B3LYP/aug-cc-pVTZ method. The agreement between observed and calculated D/H- and 15N/14N-isotopic ratios further supports these assignments. The role of this reaction in the N/O chemical network in dark interstellar clouds is discussed.

Vibrational, XRD and (13)C NMR studies of DL-phenylglycinium methanesulfonate crystal.

A new crystal formed by DL-phenylglycine and methanesulfonic acid (PGLYMS) was obtained and studied by X-ray diffraction, IR and Raman spectroscopy, solid state NMR and DSC methods. Additionally, theoretical computations for the phenylglycine cation were carried out (DFT/B3LYP/aug-cc-pVDZ). Our results show that PGLYMS does not exhibit any phase transitions and crystallizes in the P21/c space group of monoclinic system (Z=4). Detailed analysis of its structure and its IR, Raman and NMR spectra is presented.

Donor-Acceptor Complexes between Ammonia and Sulfur Trioxide: An FTIR and Computational Study.

The complexes of ammonia with sulfur trioxide have been studied using FTIR matrix isolation spectroscopy and DFT/B3LYP calculations with the aug-cc-pVTZ basis set. The NH3/SO3/Ar matrixes were prepared in two different ways. In one set of experiments the matrix was prepared by the simultaneous deposition of the NH3/Ar mixture and SO3 vapor from the thermal decomposition of K2S2O7. In the second set of experiments thermolysis products of sulfamic acid were trapped in an argon matrix. Both methods of matrix preparation led to the formation of the H3N·SO3 electron donor-acceptor complex that was characterized earlier. In the matrixes comprising thermolysis products of sulfamic acid, in addition to H3N·SO3, the H3N-SO3···NH3 complex (II(D)) was also identified. The identity of the complex was confirmed by comparison of the experimental and theoretical spectra of H3N-SO3···NH3 and D3N-SO3···ND3. The performed calculations show that in H3N-SO3···NH3 the two N atoms and the S atom are collinear; the two S-N bonds are nonequivalent, one is much shorter (2.230 Å) than the other one (2.852 Å). In the AIM topological analysis, the interaction energy decomposition and topological properties of the electron localizability indicator (ELI-D) allowed us to categorize the stronger N-S bond in the II(D) complex as a dative bond and to assume that the fragile N-S bond is a consequence of a weak electron-donor-acceptor interaction. The calculations indicate that the identified II(D) complex corresponds to a local minimum on the PES of the NH3/SO3 system of 2:1 stoichiometry. The (NH3)2SO3 complex, II(HB), corresponding to a global minimum is 7.95 kcal mol(-1) more stable than the II(D) complex. The reason that the II(D) complex is present in the matrix but not the II(HB) complex is discussed.

Isomers of the acetic acid-water complex trapped in an argon matrix.

The complexes of acetic acid (AcOH) with water have been studied using FTIR matrix isolation spectroscopy and DFT/B3LYP, DFT/B3LYP-D, and MP2 calculations with the aug-cc-pVTZ basis set. The AcOH/H2O/Ar matrices were prepared in two different ways. In one set of experiments, the vapor above a solid AcOH sample, cooled to 203 K, was diluted with H2O/Ar mixture in the vacuum chamber of the cryostat, and the mixture was solidified on the target. In the second set of experiments, the matrix was prepared by simultaneous deposition of AcOH/Ar and H2O/Ar mixtures at room temperature. The first method of matrix preparation strongly favors the formation of the "acyclic" higher energy AcOH-H2O complex I(B) compared to the second one. Warming of matrices containing the higher energy complex, I(B), from 11 to 39 K, results in the decrease of I(B) concentration and formation of the lowest energy cyclic complex I(A). The calculations indicate that I(B) is formed by an O-H···O hydrogen bond between the carbonyl oxygen and a water O-H group and, additionally, by a weak interaction between one of the methyl group hydrogen atoms and the water oxygen atom. The cyclic complex I(A) has a six-membered ring involving two O-H···O bonds. An activation energy of 0.94, 1.71, and 1.38 kcal mol(-1) was calculated for the I(B) → I(A) rearrangement at the B3LYP, B3LYP-D, and MP2 levels of theory, respectively. Van't Hoff plots for the association of H2O and AcOH leading to formation of the complexes I(A) and I(B) are presented and discussed. Evidence is also given for the formation of the AcOH-(H2O)2 and (AcOH)2-H2O complexes in the matrices. A potential atmospheric impact of the enhanced formation of the higher energy I(B) complex at low temperatures is discussed.

Clustering of simple aminosulfonic acids--electrospray ionization mass spectrometric study.

RATIONALE: Aminosulfonic acids are structurally related to amino acids as bifunctional compounds. Some of them like taurine and homotaurine play important roles in biology. Although there is a vast literature devoted to the electrospray ionization mass spectrometric (ESI-MS) study of amino acid aggregation, no such study has been performed so far for aminosulfonic acids. METHODS: A gas-phase clustering study was performed for aminomethanesulfonic acid (AMS), taurine (Tau), homotaurine (HT), and cysteic acid (CA) from water and methanol/water solutions, using a Bruker TOF-Q spectrometer equipped with an ESI source, in the negative-ion mode. For selected anionic clusters the tandem mass (MS/MS) spectra were recorded and the breakdown curves were obtained. The cluster formation abilities (ACS parameter) of the studied molecules were calculated. RESULTS: Both singly and doubly charged clusters were formed when the acids were electrosprayed from water solutions; they may be described as [(H3N-R-SO3)n-zH](z-), where z = 1 or 2. The largest identified clusters are built of 20, 22, 20 and 4 monomers of AMS, Tau, HT and CA, respectively. The doubly negatively charged clusters were observed for n ≥9, 12, 14 in the case of AMS, Tau and HT. AMS pentamers and Tau, HT tetramers and hexamers show higher stabilities than the other clusters. CONCLUSIONS: The results indicate that aminosulfonic acids form large stable clusters, similarly to aminocarboxylic acids. The cluster formation ability decreases with an increase in CH2 chain length within the series of the studied compounds. The large singly and doubly charged aggregates are formed under the conditions of the experiment, possibly in the droplets. Taurine dissolved in water seems to be a good calibrant for electrospray instruments in negative ion mode.