Photochemical reaction mechanism of cyclobutanone: CASSCF study

The photochemical reaction channels of cyclobutanone have been studied at the CASSCF level with a 6‐31G* basis set. Starting from the n‐π* excited‐state (S₁) cyclobutanone, the three reactions can take place: decarbonylation (produce CO and cyclopropane or propylene), cycloelimination (produce ketene and ethylene), and ring expansion (produce oxacarbene). Our computation indicates that decarbonylation products CO and triplet trimethylene are formed on the triplet n‐π* excited state (T₁) in a stepwise way via a biradical intermediate after intersystem crossing (ISC) to T₁ from S₁. And, then, the triplet trimethylene undergoes a second ISC to the ground state (S₀) to produce the singlet trimethylene from which cyclopropane can be produced rapidly only overcoming a 1 to 2‐kcal/mol barrier while propylene can be formed as a secondary product. The cycloelimination products ketene and ethylene are formed on the S₀ in a concerted mechanism after internal conversion (IC) to S₀ from S₁ via a biradical conical intersection. The reaction channels corresponding to ring expansion on the S₀, T₁, and S₁ states have also been discussed, and the likeliest reaction path is that oxacarbene is formed on the ground state following S₁/S₀ internal conversion. The surface topology of cyclobutanone on the S₁ surface is characterized by a transition state separating the minimum from the S₁/S₀ conical intersection, which is consistent with the previous computations and can explain the wavelength dependence of the fluorescence emission yield. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Earth-abundant Metal-catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis

Nitrogen-containing compounds, as an important class of chemicals, have been used widely in pharmaceuticals, materials synthesis. Transition metal-catalyzed reductive amination of an aldehyde or a ketone with ammonia or an amine has been proved to be an efficient and practical method for the preparation of nitrogen-containing compounds in academia and industry for a century. Given the above, several effective methods using transition metals have been developed in recent years. Noble transition metals like Pd, Pt, and Au-based catalysts have been predominately used in reductive amination. Because of their high prices, strict official regulations of residues in pharmaceuticals, and deleterious effects on the biological system, their industrial applications are severely hampered. With the increasing sustainable and environmental problems, the Earth-abundant transition metals including Ti, Fe, Co, Ni, and Zr have also been investigated for the reductive amination reaction and showed great potential to the advancement of sustainable and cost-effective reductive amination processes. This critical review will mainly summarize the work using Earth-abundant metals. The effects of different transition metals used in catalytic reduction amination were discussed and compared, and some suggestions were given. The last section highlights the catalytic activities of bi- and tri-metallic catalysts. Indeed, this latter family is very promising and simultaneously benefits from increased stability, and selectivity, compared to monometallic NPs, due to synergistic substrate activation. Few comprehensive reviews focusing on Earth-abundant transition metals catalyst has been published since 1948, although several authors reported some summaries dealing with one or the other part of this aspect. It is hoped that this critical review will inspire researchers to develop new efficient and selective earth-abundant metal catalysts for highly, environmentally sustainable reductive amination methods, as well as improve the pharmaceutical industry and related chemical synthesis company traditional method with the utilization of the green method widely.     

Fluorescent sensing system for palladium(II) based on the Heck reaction

In this paper, we report a fluorescent sensing system based on the palladium-catalyzed Heck reaction between N-methyl vinylpyridinium and 4-bromo-N,N′-dimethylaniline. Generation of a new fluorophore as a product enhances fluorescence and permits selective detection of palladium(II) among other metal species.     

Microwave pyrolysis of straw bale and energy balance analysis

The compressed wheat and corn straw bale were pyrolyzed on a microwave heating device self-designed and built with respect to the time-resolved temperature distribution, mass loss and product properties. Considering scale up and technology promotion of microwave pyrolysis (MWP), the investigations on electricity consumption and energy balance of MWP were carried out emphatically. The results indicated that MWP had obvious advantages over conventional pyrolysis, such as heating rapid and more valuable products obtained. The distribution of pyrolysis products such as gas, liquid and char was close to 1:1:1 due to the medium pyrolysis temperature and the slow heating rate, which was not favorable for the formation of gas and/or liquid products. The content of H₂ attained the highest value of 35 vol.% and syngas (H₂ and CO) was greater than 50 vol.%. The electricity consumption of MWP was between 0.58 and 0.65 kW h (kg straw)⁻¹ and with the increase of microwave power, the electricity consumption required for pyrolysis of unit mass of straw increased. The minimum microwave power for MWP was about 0.371 kW (kg straw)⁻¹ and the proportion of heat loss and conversion loss of electricity to microwave energy occupied in the total input energy was 42%. Data and information obtained are useful for the design and operation of pyrolysis of large-sized biomass via microwave heating technology.     

Rapid simultaneous determination of multiple pesticide residues in traditional Chinese medicines using programmed temperature vaporizer injection-fast gas chromatography coupled with mass spectrometry

A fast gas chromatography coupled with mass spectrometry (GC-MS) using large volume injection with programmed temperature vaporizer in solvent vent mode (PTV-LVI-SV) was developed for the trace determination of multiple pesticide residues in traditional Chinese medicines (TCMs). Experimental conditions of PTV-LVI-SV injection were optimized by central composite design. The optimized result was that initial temperature was held at 40°C for 39 s, vent flow rate was set at 45 mL/min and vent pressure was held at 0 psi for 36 s, injection volume was 10 μL. Furthermore, the quick and effective QuEChERS (quick, easy, cheap, effective, rugged and safe) method was performed to extract and purify pesticide residues in TCMs. The prepared samples were analyzed with GC-MS in the selected ion monitoring mode (SIM). The lowest LOD was 4 μg/kg for some pesticides. The recoveries were checked by spiking samples with pesticides at 25, 50 and 250 μg/kg. The average recoveries of most pesticides were from 80 to 118%. The result indicated that QuEChERS and PTV-LVI-SV GC-MS method was a rapid and sensitive analysis technique for the determination of multiple pesticide residues in TCMs.     

Induction of a High-Yield Lovastatin Mutant of Aspergillus terreus by 12C6+ Heavy-Ion Beam Irradiation and the Influence of Culture Conditions on Lovastatin Production Under Submerged Fermentation

Heavy-ion beams, possessing a wide mutation spectrum and increased mutation frequency, have been used effectively as a breeding method. In this study, the heavy-ion beams generated by the Heavy-Ion Research Facility in Lanzhou were used to mutagenize Aspergillus terreus CA99 for screening high-yield lovastatin strains. Furthermore, the main growth conditions as well as the influences of carbon and nitrogen sources on the growth and the lovastatin production of the mutant and the original strains were investigated comparatively. The spores of A. terreus CA99 were irradiated by 15, 20, 25, and 30 Gy of 80 MeV/u (12)C(6+) heavy-ion beams. Based on the lovastatin contents in the fermentation broth, a strain designated as A. terreus Z15-7 has been selected from the clone irradiated by the heavy-ion beam. When compared with the original strain, the content of lovastatin in the fermentation broth of A. terreus Z15-7 increased 4-fold. Moreover, A. terreus Z15-7 efficiently used the carbon and nitrogen sources for the growth and production of lovastatin when compared to the original strain. The maximum yield of lovastatin, 916.7 μg/ml, was obtained as A. terreus Z15-7 was submerged cultured in the chemically defined medium supplemented with 3% glycerol as a carbon source, 1% corn meal as an organic nitrogen source, and 0.2% sodium nitrate as an inorganic nitrogen source at 30 °C in the shake flask. The result shows that heavy-ion beam irradiation is an effective method for the mutation breeding of lovastatin production of A. terreus.     

Resonance Rayleigh scattering spectra, non-linear scattering spectra of malachite green-12-tungstophosphoric acid system and its analytical application in fish

In 0.1 molL(-1) (pH 1.0) HCl medium, 12-tungstophosphoric acid (TP) reacted with malachite green (MG) to form an ion-association complex. As a result, the new spectra of RRS, SOS and FDS appeared and their intensities were enhanced greatly. The maximum wavelengths of RRS, SOS and FDS were located at 334 nm, 586 nm and 330 nm, and the scattering intensities were proportional to the concentration of MG. Based on it a new method for the determination of MG has been established. The detection limits (3σ) of these methods were in the range of 3.7-27 ng mL(-1). The RRS, SOS, and FDS characteristics, absorption spectrum characteristics and optimum reaction conditions of the system were discussed. Effects of coexistent substances were tested, and the results demonstrated that this method had good selectivity. It has been applied to the determination of malachite green residues in fish flesh with satisfactory results. The reaction mechanism and reasons of RRS enhancement are discussed.     

Formation of metal complex ions from amino acid in the presence of Li+, Na+ and K+ by electrospray ionization: metal replacement of hydrogen in the ligands

Alkali metal cations easily form complexes with proteins in biological systems; understanding amino acid clusters with these cations can provide useful insight into their behaviors at the molecular level including diagnosis and therapy of related diseases. For the purpose of characterization of basic interaction between amino acids and alkali metal, each of the 20 naturally occurring amino acids were ionized in the presence of lithium, sodium and potassium cations by electrospray ionization, and the resulting product ions were analyzed. We focus our attention on the gas phase alkali metal ion-proton exchanged complexes in current study, specifically complexes with serine, threonine, asparagine and glutamine, which share characteristic pattern unlike other amino acids. All amino acids generated [M + H](+) and [M + Na](+) ions, where M stands for the neutral amino acid. Serine, threonine, asparagine and glutamine generated cluster ions of [nM - nH + (n + 1)Na](+) and [nM - (n - 1)H + (n - 1)Na + K](+) , where n = 1-7. While the (M - H + Li) and (M - H + K) species were not observed, the neutral (M - H + Na) species formed by proton-sodium cation exchange had a highly stable cyclic structure with ketone and amine ligand sites, suggesting that (M - H + Na) serves as a building block in cluster ion formation. Cluster ion intensity distributions of [nM - nH + (n + 1)Na](+) and [nM - (n - 1)H + (n - 1)Na + K](+) showed a magic number at n = 3 and 4, respectively. Extensive B3LYP-DFT quantum mechanical calculations were carried out to elucidate the geometry and energy of the cluster ions, and they provided a reasonable explanation for the stability and structure of the cluster ions.     

Two octacyanometallate-based Ni(II)W(V) bimetallic assemblies with metamagnetism

Reactions of the precursors [Ni(macrocyclic ligand)](2+) with [W(CN)(8)](3-) afford two octacyanotungstate-based assemblies, (H(2)L(1))(0.5)[Ni(L(1))][W(CN)(8)]·2DMF·H(2)O (L(1) = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) (1) and [Ni(L(2))](3)[W(CN)(8)](2)·4H(2)O (L(2) = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) (2). Single crystal X-ray diffraction shows that 1 consists of anionic one-dimensional (1D) linear chains, while 2 is built of 2D graphite-like layers with (6, 3) topology. Magnetic studies reveal that both complexes exhibit metamagnetic behavior from the spin-canted antiferromagnet to the ferromagnet induced by field.