Chemical mass shifts in resonance ejection experiments in the quadrupole ion trap

Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions.     

Agreement between experiment and hybrid DFT calculations for O--H bond dissociation enthalpies in manganese complexes

Information on the accuracy of DFT functionals for redox reactions in transition metal systems is rather limited. To analyze the performance of some popular functionals for redox reactions in manganese systems, calculated O--H bond dissociation enthalpies for Mn-ligands in six different complexes are compared to experimental results. In this benchmark, B3LYP performs well with a mean absolute error of 3.0 kcal/mol. B98 gives similar results to B3LYP (error of 3.8 kcal/mol). B3LYP* gives lower O--H bond strengths than B3LYP and has a mean error of 5.0 kcal/mol. Compared to B98 and B3LYP, B3LYP* has an error trend for the manganese ligands that is more similar to the error for a free water molecule. The nonhybrid functional BLYP consistently and significantly underestimates the O--H bond strengths by approximately 20 kcal/mol. HCTH407 has a rather large mean error of 9.4 kcal/mol and shows no consistent trend. The results support the use of hybrid functionals and the present computational method for large model systems containing manganese. An example is the oxygen evolving complex in photosystem II where hybrid functionals predict the appearance of a Mn(IV)-oxyl radical before the O--O bond formation step.     

Can semi-empirical models describe HCl dissociation in water?

We discuss the failure of commonly used AM1 and PM3 semiempirical methods to correctly describe acid dissociation. We focus our analysis on HCl because of its physicochemical importance and its relevance in atmospheric chemistry. The structure of non-dissociated and dissociated HCl – (H₂O) _n clusters is accounted for. The very bad results obtained with PM3 (and also with AM1) are related to large errors in gas-phase proton affinity of water and gas-phase acidity of HCl. Indeed, estimation of pKa values shows that neither AM1 nor PM3 are able to predict HCl dissociation in liquid water since HCl is found to be a weaker acid than H₃O⁺. We have proposed in previous works a modified PM3 approach (PM3-MAIS) adapted to intermolecular calculations. It is derived from PM3 by reparameterization of the core–core functions using ab initio data. Since parameters for H–Cl and O–Cl core–core interactions were not yet available, we have carried out the corresponding optimization. Application of the PM3-MAIS method to HCl dissociation in HCl–(H₂O) _n clusters leads to a huge improvement over PM3 results. Though the method predicts a slightly overestimated HCl acidity in water environment, the overall agreement with ab initio calculations is very satisfying and justifies efforts to develop new semiempirical methods.     

The dissociation quotients of formic acid in sodium chloride solutions to 200°C

The dissociation quotients of formic acid were measured potentiometrically from 25 to 200°C in NaCl solutions at ionic strengths of 0.1, 0.3 1.0, 3.0, and 5.0 mol-kg^–1. The experiments were carried out in a concentration cell with hydrogen electrodes. The resulting molal acid dissociation quotients for formic acid, as well as a set of infinite dilution literature values and a calorimetrically-determined enthalpy of reaction, were fitted by an empirical equation involving an extended Debye Hückel term and seven adjustable parameters involving functions of temperature and ionic strength. This regressional analysis yielded the following thermodynamic quantities for 25°C: logK=–3.755±0.002, H^o=–0.09±0.15 kJ-mol^–1, S^o=–72.2±0.5 J-K^–1-mol^–1, and C _p ^o =–147±4 J-K^–1-mol^–1. The isocoulombic form of the equilibrium constant is recommended for extrapolation to higher temperatures.     

Electrical Conductance and Volumetric Studies in Aqueous Solutions of DL-Pyroglutamic Acid

Conductivity measurements of DL-pyroglutamic acid and sodium pyroglutamate in dilute aqueous solutions were performed in the 288.15–323.15 K temperature range. The limiting molar conductances of pyroglutamate anion, λ^o(pGlu⁻, T) and the dissociation constants of pyroglutamic acid, K(T) were derived from the Onsager, and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.5 mol-kg⁻¹ were determined at 5 K intervals from T = 288.15 K to 333.15 K. Densities served to evaluate the apparent molar volumes, V_2,φ(m, T), the cubic expansion coefficients, α (m,T) and the changes of the isobaric heat capacities with respect to pressure, (∂ C_P/∂ P)_T,m. They were correlated qualitatively with the changes in the structure of water when pyroglumatic acid is dissolved in it.     

环境污染物中碳氯键离解能的理论研究

利用六种密度泛函理论方法（B3LYP, B3P86, MPW1K, TPSS1KCIS, X3LYP, BMK）对碳氯键离解能进行理论计算,结果发现几种新发展的密度泛函(DFT)方法用于碳氯键离解能的计算比传统的B3LYP有较大的改善,其中对能量估算相对准确的B3P86方法对碳氯键离解能的计算精度最高,对17个分子中碳氯键离解能计算的平均绝对偏差为6.58 kJ/mol。最后运用B3P86方法对一系列环境危害较大,但可通过光化学降解和生物降解的氯代有机物的碳氯键离解能值进行预测,并讨论了影响碳氯键离解能的结构性质关系。     

Microscale Thermophoresis and Molecular Modelling to Explore the Chelating Drug Transportation in the Milk to Infant

The microscale thermophoresis (MST) technique was utilized to investigate lactoferrin–drug interaction with the iron chelator, deferiprone, using label-free system. MST depends on the intrinsic fluorescence of one interacting partner. The results indicated a significant interaction between lactoferrin and deferiprone. The estimated binding constant for the lactoferrin–deferiprone interaction was 8.9 × 10⁻⁶ ± 1.6, SD, which is to be reported for the first time. Such significant binding between lactoferrin and deferiprone may indicate the potentiation of the drug secretion into a lactating mother’s milk. The technique showed a fast and simple approach to study protein–drug interaction while avoiding complicated labeling procedures. Moreover, the binding behavior of deferiprone within the binding sites of lactoferrin was investigated through molecular docking which reflected that deferiprone mediates strong hydrogen bonding with ARG121 and ASP297 in pocket 1 and forms H-bond and ionic interaction with ASN640 and ASP395, respectively, in pocket 2 of lactoferrin. Meanwhile, iron ions provide ionic interaction with deferiprone in both of the pockets. The molecular dynamic simulation further confirmed that the binding of deferiprone with lactoferrin brings conformational changes in lactoferrin that is more energetically stable. It also confirmed that deferiprone causes positive correlation motion in the interacting residues of both pockets, with strong negative correlation motion in the loop regions, and thus changes the dynamics of lactoferrin. The MM-GBSA based binding free energy calculation revealed that deferiprone exhibits ∆G TOTAL of −63,163 kcal/mol in pocket 1 and −63,073 kcal/mol in pocket 2 with complex receptor–ligand difference in pocket 1 and pocket 2 of −117.38 kcal/mol and −111.54 kcal/mol, respectively, which in turn suggests that deferiprone binds more strongly in the pocket 1. The free energy landscape of the lactoferrin–deferiprone complex also showed that this complex remains in a high energy state that confirms the strong binding of deferiprone with the lactoferrin. The current research concluded that iron-chelating drugs (deferiprone) can be transported from the mother to the infant in the milk because of the strong attachment with the lactoferrin active pockets.     

Regge Models of Proton Diffractive Dissociation Based on Factorisation and Structure Functions

Recent results by the authors on proton diffractive dissociation (single, double and central) in the low-mass resonance region with emphasis on the LHC kinematics are reviewed and updated. Based on the previous ideas that the contribution of the inelastic proton–Pomeron vertex can be described by the proton structure function, the contribution of the inelastic Pomeron–Pomeron vertex appearing in central diffraction is now described by a Pomeron structure function.     

甲基羟基铀酰离子与水的复分解反应

以醋酸铀酰为主要试剂, 在负离子检测模式下, 采用电喷雾串联质谱法制备了甲基羟基铀酰负离子. 实验发现, 气相中的甲基羟基铀酰离子与水分子发生分子离子复分解反应, 并用串联质谱法对反应产生的离子性产物进行了结构确认, 提出了反应的可能机理. 热力学计算结果表明, 该反应的ΔGReaction为-473.0 kJ/mol, ΔHReaction为-236.5 kJ/mol, ΔSSystem为0.792 kJ·mol-1·K-1. 该反应的速率常数为2.26 s-1.     

Sensing the ortho Positions in C6Cl6 and C6H4Cl2 from Cl2− Formation upon Molecular Reduction

The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl₂⁻. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using ortho-, meta- and para-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl₂⁻ formation can only occur in 1,2-C₆H₄Cl₂, where the two closest C–Cl bonds are cleaved while the chlorine atoms are brought together within the ring framework due to excess energy dissipation. These results show that a strong coupling between electronic and C–Cl bending motion is responsible for a positional isomeric effect, where molecular recognition is a determining factor in chlorine anion formation.