Theoretical study of the CH2 + O photodissociation of formaldehyde adsorbed on the Ag(111) surface

Configuration interaction calculations of the ground and excited states of the H2CO molecule adsorbed on the Ag(111) surface have been carried out to study the photoinduced dissociation process leading to polymerization of formaldehyde. The metal-adsorbate system has been described by the embedded cluster and multireference configuration interaction methods. The pi electron-attachment H2CO- and n-pi* internally excited H2CO* states have been considered as possible intermediates. The calculations have shown that H2CO* is only very weakly bound on Ag(111), and thus that the dissociation of adsorbed formaldehyde due to internal excitation is unlikely. By contrast, the H2CO- anion is strongly bound to Ag(111) and gains additional vibrational energy along the C-O stretch coordinate via Franck-Condon excitation from the neutral molecule. Computed energy variations of adsorbed H2CO and H2CO- at different key geometries along the pathway for C-O bond cleavage make evident, however, that complete dissociation is very difficult to attain on the potential energy surface of either of these states. Instead, reneutralization of the vibrationally excited anion by electron transfer back to the substrate is the most promising means of breaking the C-O bond, with subsequent formation of the coadsorbed O and CH2 fragments. Furthermore, it has been demonstrated that the most stable state for both dissociation fragments on Ag(111) is a closed-shell singlet, with binding energies relative to the gas-phase products of approximately 3.2 and approximately 1.3 eV for O and CH2, respectively. Further details of the reaction mechanism for the photoinduced C-O bond cleavage of H2CO on the Ag(111) surface are also given.     

Cationic Porphyrin-Graphene Oxide Hybrid: Donor-Acceptor Composite for Efficient Photoinduced Electron Transfer

Non-covalent nanohybrids composed of cationic 5,10,15,20-tetra(4-trimethylammoniophenyl)porphyrin tetra(p-toluenesulfonate) (TMAP) and the graphene oxide sheets were prepared under two pH values (6.2 vs. 1.8). The TMAP molecule was positively charged, regardless of the pH value during preparation. However, protonation of the imino nitrogens increased the overall charge of the porphyrin molecule from +4 to +6 (TMAP⁴⁺ and TMAP⁶⁺). It was found that at acidic pH, interaction of TMAP⁶⁺ with GO was largely suppressed. On the other hand, results of FTIR, Raman spectroscopy, thermogravimetric analysis, atomic force microscopy (AFM) and elemental analysis confirmed effective non-covalent functionalization of graphene oxide with cationic porphyrin at pH 6.2. The TMAP⁴⁺-GO hybrids exhibited well defined structure with a monolayer of TMAP⁴⁺ on the GO sheets as confirmed by AFM. Formation of the ground-state TMAP⁴⁺-GO complex in solution was monitored by the red-shift of the porphyrin Soret absorption band. This ground-state interaction between TMAP⁴⁺ and GO is responsible for the static quenching of the porphyrin emission. Fluorescence was not detected for the nanohybrid which indicated that a very fast deactivation process had to take place. Ultrafast time-resolved transient absorption spectroscopy clearly demonstrated the occurrence of electron transfer from the photoexcited TMAP⁴⁺ singlet state to GO sheets, as proven by the formation of a porphyrin radical cation.     

Simulation of heterogeneous end-coupling reactions in polydisperse polymer blends

The influence of polydispersity on the interfacial kinetics of end-coupling and microstructure formation in the melt of immiscible polymers was studied using dissipative particle dynamics simulations. The irreversible reaction started at a flat interface between two layers, each of which contained polymer chains of two different lengths with functionalized or unreactive end groups. As in the case of fully functionalized monodisperse reactants [A. V. Berezkin and Y. V. Kudryavtsev, Macromolecules 44, 112 (2011)], four kinetic regimes were observed: linear (mean field coupling at the initial interface), saturation (decreasing the reaction rate due to the copolymer brush formation or reactant depletion near the interface), autocatalytic (loss of the initial interface stability and formation of a lamellar microstructure), and terminal (microstructure ripening under diffusion control). The interfacial instability is caused by overcrowding the interface with the reaction product, and it can be kinetically suppressed by increasing chain length of the reactants. Main effects of polydispersity are as follows: (i) the overall end-coupling rate is dominated by the shortest reactive chains; (ii) the copolymer concentration at the interface causing its instability can be not the same as in the lamellas formed afterwards; (iii) mean length of the copolymer product considerably changes with conversion passing through a minimum when a microstructure is just formed.     

Synthesis of Functionalized Isoquinolone Derivatives via Rh(III)-Catalyzed [4+2]-Annulation of Benzamides with Internal Acetylene-Containing α-CF3-α-Amino Carboxylates

A convenient pathway to a new series of α-CF₃-substituted α-amino acid derivatives bearing pharmacophore isoquinolone core in their backbone has been developed. The method is based on [4+2]-annulation of N-(pivaloyloxy) aryl amides with orthogonally protected internal acetylene-containing α-amino carboxylates under Rh(III)-catalysis. The target annulation products can be easily transformed into valuable isoquinoline derivatives via a successive aromatization/cross-coupling operation.     

Development of the Microemulsion Electrokinetic Capillary Chromatography Method for the Analysis of Disperse Dyes Extracted from Polyester Fibers

The study aimed to develop a method for the separation of dispersed dyes extracted from polyester fibers. Nine commercially available disperse dyes, which were used to dye three polyester fabrics, were tested. Extraction of dyes from 1 cm long threads was carried out in chlorobenzene at 100 °C for 6 h. The separation was performed using microemulsion electrokinetic capillary chromatography (MEEKC) with photodiode array detection. Microemulsion based on a borate buffer with an organic phase of n-octane and butanol and a mixture of surfactants, sodium dodecyl sulphate and sodium cholate, were used. The addition of isopropanol and cyclodextrins to microemulsion resulted in a notable improvement in resolution and selectivity. The content of additives was optimized by using the Doehlert experimental design. Values of the coefficient of variance obtained in the validation process, illustrating the repeatability and intermediate precision of the migration times fit in the range of 0.11–1.24% and 0.58–3.21%, respectively. The developed method was also successfully applied to the differentiation of 28 real samples—polyester threads collected from clothing. The obtained results confirmed that proposed method may be used in the discriminant analysis of polyesters dying by disperse dyes and is promisingly employable in forensic practice.     

Antibody–Ferrocene Conjugates as a Platform for Electro-Chemical Detection of Low-Density Lipoprotein

Low-density lipoprotein (LDL) is a cardiac biomarker identified in the pathology of cardiovascular disease (CVD). Typically, the level of LDL is calculated using the Friedewald relationship based on measured values of total cholesterol, high-density lipoproteins (HDL), and triglycerides. Unfortunately, this approach leads to some errors in calculation. Therefore, direct methods that can be used for fast and accurate detection of LDL are needed. The purpose of this study was to develop an electrochemical platform for the detection of LDL based on an antibody–ferrocene conjugate. An anti-apolipoprotein B-100 antibody labeled with ferrocene was covalently immobilized on the layer of 4-aminothiophenol (4-ATP) on the surface of gold electrodes. Upon interaction between LDL and the antibody–ferrocene conjugate, a decrease in the ferrocene redox signal registered by square wave voltammetry was observed, which depends linearly on the concentration from 0.01 ng/mL to 1.0 ng/mL. The obtained limit of detection was equal to 0.53 ng/mL. Moreover, the satisfied selectivity toward human serum albumin (HSA), HDL, and malondialdehyde-modified low-density lipoprotein (MDA-LDL) was observed. In addition, the acceptable recovery rates of LDL in human serum samples indicate the possible application of immunosensors presented in clinical diagnostics.     

2' And 3'-ketonucleosides and their arabino and xylo reduction products: Convenient access via selective protection and oxidation of ribonucleosides

A number of 2',5'- or 3',5'-diprotected ribonucleosides and 5'-protected 2'- or 3'-deoxy-β-D-erythro-pentofuranosyl nucleosides have been oxidized to the corresponding 3' or 2'-ketonucleoside derivatives using chromium trioxide/pyridine/acetic anhydride or dimethyl sulfoxide/ acetic anhydride. Reduction of the carbonyl functions with sodium borohydride gave the inverted arabino, xylo, or deoxy-threo isomers as predominant products by attack at the less hindered α-face of the sugar ring. Parallel reductions using sodium borodeuteride corroborated the epimeric ratios by demonstrating that complete oxidation of the original hydroxyl groups had occurred. The deuterium labeling also aided in making NMR spectral assignments.     

Methyltrifluoropyruvate imines possessing N-oxalyl and N-phosphonoformyl groups--precursors to a variety of alpha-CF3-alpha-amino acid derivatives

Convenient routes to methyl 2-oxalylimino- and 2-(phosphonoformimido)-3,3,3-trifluoropropanoates have been elaborated, based on the reaction of methyl trifluoropyruvate with ethyl oxamate or diethyl carbamoylphosphonate, respectively, followed by dehydration. The compounds obtained are useful synthetic intermediates toward a variety of novel 3,3,3-trifluoroalanine derivatives that are potential drug candidates.     

Raman spectroscopy of smithsonite

Raman spectroscopy at both 298 and 77 K has been used to study a series of selected natural smithsonites from different origins. An intense sharp band at 1092 cm⁻¹ is assigned to the CO₃²⁻ symmetric stretching vibration. Impurities of hydrozincite are identified by a band around 1060 cm⁻¹. An additional band at 1088 cm⁻¹ which is observed in the 298 K spectra but not in the 77 K spectra is attributed to a CO₃²⁻ hot band. Raman spectra of smithsonite show a single band in the 1405–1409 cm⁻¹ range assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional bands for the ν₃^g modes for some smithsonites is significant in that it shows distortion of the ZnO₆ octahedron. No ν₂ bending modes are observed for smithsonite. A single band at 730 cm⁻¹ is assigned to the ν₄ in phase bending mode. Multiple bands be attributed to the structural distortion are observed for the carbonate ν₄ in phase bending modes in the Raman spectrum of hydrozincite with bands at 733, 707 and 636 cm⁻¹. An intense band at 304 cm⁻¹ is attributed to the ZnO symmetric stretching vibration. Copyright © 2007 John Wiley & Sons, Ltd.