High-Resolution Infrared Synchrotron Investigation of (HCN)2 and a Semi-Experimental Determination of the Dissociation Energy D0

The high-resolution infrared absorption spectrum of the donor bending fundamental band ν of the homodimer (HCN)₂ has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν transition has the typical appearance of a perpendicular type band associated with a Σ–Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν₀ of 779.05182(50) cm⁻¹ together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm⁻¹ relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol⁻¹. The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19 , 3257–3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol⁻¹ for the dissociation energy D₀ of this prototypical homodimer.     

An efficient preparation of vinamidinium hexafluorophosphate salts

Substituted acetic acids or acetyl chlorides react with phosphorus oxychloride in DMF to yield the vinamidinium salts 3a-j in moderate to excellent recrystallized yields (28-90%). The cations are conveniently isolated as their hexafluorophosphate salts, which are easily handled nonhygroscopic solids. The nitro compound 3l is prepared in 91% yield by nitration of the parent vinamidinium 3k. The X-ray crystal structure is reported for the 2-phenyl isomer 3e and displays minimal overlap of the two pi-systems.     

222RN at Bermuda and Mauna Loa: Local and distant sources

Continuous measurements of atmospheric²²²Rn were made for the past three years by the Environmental Measurements Laboratory (EML) at the Atmosphere/Ocean Chemistry Experiment site located at Tudor Hill, Bermuda and at the National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory Mauna Loa Observatory. The²²²Rn analyzer is based on the two-filter tube method. At the Bermuda site, monthly median²²²Rn concentration range from 50 to 700 mBq m^–3, and the concentrations vary seasonally, with a maximum in the winter and a minimum in the summer. The concentrations are significantly elevated when local winds traverse the island. At MLO, monthly median²²²Rn concentrations range from 100 mBq m^–3 during the fall months to 400 mBq m^–3 during the spring months. The springtime maximum values correspond to periods of rapid transport in the free troposphere from the Asian continent, corroborated by backward air mass trajectories. The²²²Rn data are also used to help decipher local daily upslope/downslope conditions present at MLO. This study illustrates the value of atmospheric²²²Rn monitoring, when screened through the filter of local meteorology, in studying the transport of continental air to the oceans, as well as the dynamics of local meteorological effects.     

Synthesis of α-2′-deoxynucleosides

α-Thymidine (4) was synthesized from thymidine (1) in 3 steps in 36% overall yield without using chro-matography and with the possibility of increasing the yield to 85% by reusing the remaining α,β-mixture. 1-(2-Deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl)thymine (3) was further converted to 1-(2-deoxy-α-D-erythro-pentofuranosyl)-5-methylcytosine (5) .     

Characterization of poly(3,4-ethylenedioxythiophene):tosylate conductive polymer microelectrodes for transmitter detection

In this paper we investigate the physical and electrochemical properties of micropatterned poly(3,4-ethylenedioxythiophene):tosylate (PEDOT:tosylate) microelectrodes for neurochemical detection. PEDOT:tosylate is a promising conductive polymer electrode material for chip-based bioanalytical applications such as capillary electrophoresis, high-performance liquid chromatography, and constant potential amperometry at living cells. Band electrodes with widths down to 3 μm were fabricated on polymer substrates using UV lithographic methods. The electrodes are electrochemically stable in a range between -200 mV and 700 mV vs. Ag/AgCl and show a relatively low resistance. A wide range of transmitters is shown to oxidize readily on the electrodes. Kinetic rate constants and half wave potentials are reported. The capacitance per area was found to be high (1670 ± 130 μF cm(-2)) compared to other thin film microelectrode materials. Finally, we use constant potential amperometry to measure the release of transmitters from a group of PC 12 cells. The results show how the current response decreases for a series of stimulations with high K(+) buffer.     

Crystal structure of a partly self-complementary peptide nucleic acid (PNA) oligomer showing a duplex-triplex network

The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks.     

Influence of β‐Cyclodextrin on the Mixed Micellization Process of Sodium Dodecyl Sulfate and Sodium Lauroyl Sarcosine and Formation of Inclusion Complexes

In this work, we have studied the influence of different concentrations of β‐Cyclodextrin (β‐CD) on the mixed micellization of anionic surfactants sodium dodecyl sulfate (SDS) and sodium lauroyl sarcosine (SLAS) at different SDS mole fractions (α_SDS). From conductivity data, the critical micellar concentration (cmc), the equivalent ionic conductivities of the monomeric species (Λ_m), the associated species (Λ_assc) and the micelle (Λ_mic), the degree of counterion dissociation (α) in the presence of β‐CD were evaluated from the slope of the conductivity versus concentration plots for the pure and binary mixtures. The apparent cmc of the surfactants vary linearly with the β‐CD concentrations. From the dependence of cmc of the surfactants on β‐CD concentration, we have deduced the association constant (K) of surfactant‐β‐CD inclusion complexes assuming 1∶1 stoichiometry. Theories of Clint, Regular solution, and Motomura's have been used for the evaluation of ideality or nonideality of the mixed system. Mixed micelles were found to be rich in SDS content at the cmc in the presence and the absence of β‐CD. The cmc values have been used to evaluate the transfer of standard free energy of micelles (ΔG⁰ _M,tr) from the aqueous medium to additive medium.     

Interactions of γ-Cyclodextrin with the Mixed Micelles of Anionic Surfactants and Their Inclusion Complexes Formation

Interactions of γ-cyclodextrin (γ-CD) with the single and mixed micelles of sodium dodecyl sulfate (SDS) and sodium lauroyl sarcosine (SLAS) have been studied at different concentrations of γ-CD by using conductivity measurements. From conductivity data, the pure and mixed critical micellar concentration (cmc), the equivalent ionic conductivities of the monomeric species (Λ _m), the associated species (Λ _assc) and the micelle (Λ _mic), the degree of counterion dissociation (χ) in the presence of γ-CD have been evaluated from the slope of the conductivity versus concentration plots for the pure and binary mixture of surfactants. From the dependence of cmc of the surfactantson γ-CD concentration, we have deduced the association constant (K) of surfactant-γ-CD inclusion complexes assuming 2:1 stoichiometry. Theories of Clint, regular solution, and Motomura's have been used for the evaluation of ideality or nonideality of the mixed system. Mixed micelles were found to be rich in SDS content in the presence and the absence of γ-CD. The cmc values have been used to evaluate the transfer of standard free energy of micelles (ΔG⁰ _M,tr) from the aqueous medium to additive medium.     

Sample preparation for high throughput accurate mass analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

An automated sample preparation for high throughput accurate mass determinations by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been developed. Sample preparation was performed with an automated workstation and automated mass analyses were performed with a commercial MALDI-TOF mass spectrometer. The method was tested with a 41-sample library. MALDI-TOFMS was found to give the needed sensitivity, accurate mass measurement, and soft ionization necessary for structure confirmation, even of mixtures. A mass accuracy of 5 ppm or less was obtained in over 80% of known compound measurements. A mass accuracy better than 10 ppm was obtained for all measurements of known compounds. Analyses of parallel synthesis products resulted in 77% of the measurements with a mass accuracy of 5 ppm or better.