Stereospecific Formation of the rctt Isomer of Bis-crown-Containing Cyclobutane upon [2 + 2] Photocycloaddition of an (18-Crown-6)stilbene Induced by Self-Assembly via Hydrogen Bonding.

The formation and the spectroscopic and structural properties of 1:1 and 2:1 (ligand-to-dication) complexes of an (18-crown-6)stilbene with ethane-1,2-diammonium diperchlorate in MeCN were studied by UV-vis and NMR spectroscopy and by density functional theory calculations. Prolonged UV irradiation of 2:1 mixtures of the crown stilbene and the diammonium salt led to the formation of two main photoproducts, namely, the single syn-"head-to-head" photodimer of the crown stilbene (rctt cyclobutane) due to supramolecular-assisted [2 + 2] photocycloaddition and a crown ether derivative of phenanthrene due to a photoinduced electrocyclization reaction. The rctt cyclobutane was isolated by preparative photolysis, followed by chromatography. The selectivity of the [2 + 2] photocycloaddition is explained by supramolecular pre-organization of crown stilbene molecules into the 2:1 complexes that have a pseudo-sandwich structure with stacking interactions between the stilbene moieties.

Ionization of organic molecules with metal ions formed in the laser plasma.

A laser plasma ion source was used to ionize volatile organic compounds in a gas sample. The plasma was generated on a metal target in the intermediate vacuum region of ~0.3 Torr using a pulsed Nd:YAG laser with a wavelength of 1 µm. The resulting ions mass spectra were acquired using orthogonal time-of-flight mass spectrometer (O-TOF MS). When using a copper target, the ions formed are simple complexes (CuM+ ) of copper ions with organic molecules. The possibility of online identification of trace amounts of alkanes in nitrogen and air, with a detection limit of ~10 ppb, was demonstrated. The ionization efficiency of volatile organic compounds through the formation of clusters with metal ions is 10-4 in terms of the quasimolecular complex ions. The rate constants of ion-molecular reactions of copper ions with octane and water molecules in nitrogen and air are estimated.

Two possible improvements for mass spectrometry analysis of intact biomolecules.

The goals of our study were to investigate abilities of two approaches to eliminate possible errors in electrospray mass spectrometry measurements of biomolecules. Passing of a relatively dense supersonic gas jet through ionization region followed by its hitting the spray of the analyzed solution in low vacuum may be effective to keep an initial biomolecule structure in solution. Provided that retention of charge carriers for some sites in the biomolecule cannot be changed noticeably in electrospray ion source, decomposition and separation of charge-state distributions of electrosprayed ions may give additional information about native structure of biomolecules in solution.

Numerical simulation of ion transport in an atmosphere-to-vacuum interface taking into account gas dynamics and space charge.

A two-step approach was developed for the study of ion transport in an atmospheric pressure interface. In the first step, the flow in the interface was numerically simulated using the standard gas dynamic package ANSYS CFX 15.0. In the second step, the calculated fields of pressure, temperature, and velocity were imported into a custom-built software application for simulation of ion motion under the influence of both gas dynamic and electrostatic forces. To account for space charge effects in axially symmetric interfaces an analytical expression was used for the Coulomb force. For all other types of interfaces, an iterative approach for the Coulomb force computation was developed. The simulations show that the influence of the space charge is the main contributor to the loss of ion current in the heated capillary. In addition, the maximum ion current which can be transmitted through the heated capillary (0.58 mm inner diameter and 58.5 mm length) is limited to ∼6 nA for ions with m/z = 508 Da and with reduced ion mobility 1.05 cm2V-1s-1. This limit remains practically constant and independent of the ion current at the entrance of the capillary. For a particular ion type, this limit depends on its m/z ratio and ion mobility.