Synthesis of mono meso-pyridyl 21,23-dithiaporphyrins and unsymmetrical non-covalent porphyrin dimers

A new method has been developed to synthesize 21,23-dithiaporphyrins having one pyridyl group at the meso position. The method required easily available unknown precursors and the condensation resulted in mono meso-pyridyl 21,23-dithiaporphyrins as single products in 8-11% yield. Two of the three mono meso-pyridyl N₂S₂ porphyrins were used to synthesize non-covalent unsymmetrical porphyrin dimers containing one N₂S₂ and one N₄ porphyrin cores.     

Indole 3-alkylation/vinylation under catalysis of the guanidinium ionic liquids

Two ionic liquids, N,N,N,N-tetramethylguanidinium trifluoroacetate (TMGT) and the unprecedented N,N,N,N-tetramethylguanidinium triflate (TMGT_f), were used as catalyst solvents in condensations between indoles and arylaldehydes or 1,3-diketones providing a simple and efficient method for synthesis of bis(3-indolyl)methanes or casually 3-alkenylindoles due to stereoelectronic concerns of reactants. The ionic liquids are easily separated and reused for several times.     

Equilibrium convoy electron production and charge exchange

RatiosN _2s /N _3p of 2s to 3p populations in hydrogen atoms formed by the passage of protons through carbon foils have been measured using the beam-foil-laser excitation method reported very recently. No dependence ofN _2s /N _3p on the incident proton energyE _p , in the 100–300 keV energy range analysed, is observed. From the ratioN _3p /N _2p of 3p to 2p beam-foil populations in hydrogen reported previously (N _3p /N _2p independent ofE _p forE _p >100 keV) and the ratiosN _2s /N _3p measured in the present work, a mean value ofN _2s /N _2p equal to 0.61±0.04 is deduced. These results are compared with available experimental data.     

An efficient method for the calculation of generalized overlap amplitudes for core photoelectron shake-up spectra

Using a Gelfand-Tsetlin N-electron basis and a graphical unitary group approach, an efficient method is derived for the calculation of generalized overlap amplitudes of the formX⁽ⁿ⁾_p = < Ψ⁽ⁿ⁾)(N-1) ¦ψa_p¦ψ⁽⁰⁾ (N) >, whereψ⁽ⁿ⁾(N-1) and ψ⁽⁰⁾(N) denote complete active space wavefunctions and p is a core orbital index. Using this method the computational effort to obtain Xⁿ_p is negligible compared to the wavefunction optimization.     

A new approach to binary tree-based heuristics

The goals and limitations of some clustering methods are briefly reviewed. In order to avoid the usual methods which are very demanding on computer time and space, a new scheme is proposed for updating (generation) of, and retrieval from, large data bases organized as binary trees. The method is based on calculation of three distances at any given vertex l on the level n, A(l,n) instead of two. The respective distances d₁(X,A_l), d₂(X,A_r), d₃(A_lA_r) are calculated between the input vector X and the left and right descendant of the vertex A(l,n), A_l and A_r, respectively. The advantage of the method compared to the standard clustering methods or formation of hierarchal trees is that the required memory or computational time is reduced from N² to approximately N log N (N is the number of clustering objects).     

Practical and versatile oxidation of alcohol using novel Na2WO4–H2O2 system under neutral conditions

This paper presents a novel Na₂WO₄–H₂O₂ oxidation system. The oxidation of alcohol to ketone or aldehyde was carried out by using N,N-dimethylacetamide, hydrogen peroxide, and a catalytic amount of disodium tungstate dihydrate under neutral conditions. This method is very simple, practical for large-scale manufacturing, and applicable to a variety of substrates including an acid-sensitive substrate. Disodium tetraperoxotungstate dihydrate (Na₂[W(O₂)₄]·2H₂O) was isolated from a mixture of N,N-dimethylacetamide, hydrogen peroxide, and disodium tungstate dihydrate, and a proposal reaction mechanism is discussed in this paper.     

Thermal electronic properties of alkali clusters

We apply the finite-temperature Kohn-Sham method to alkali metal clusters, using the spherical jellium model and treating the valence electrons as a canonical system in the heat bath of the ions. We study the shell effects in the total free energyF(N) and the entropyS(N) for neutral clusters containingN atoms. Their strongest temperature dependence is due to the finite ground-state valueS ₀>0 of the electronic entropy for non-magic clusters. It leads to a decreasing amplitude and an increasing smear-out of the saw-tooth structure in the first difference Δ₁ F(N)=F(N?1)?F(N) with increasing temperatureT and cluster sizeN.     

Synthesis of novel 2-phenyl-5-substituted dihydropyrimidines using 2-phenyl-1,3-diaza-1,3-butadienes and electron-deficient olefins

A novel synthetic method for 2,5-disubstituted dihydropyrimidines was developed. The cyclization of 1,3-diaza-4-dimethylamino-1,3-butadienes having a N-protecting group (N-Boc, N-Cbz, N-n-C₄H₉, N-Bn or N-Ph) with electron-deficient olefins, such as α,β-unsaturated carbonyl compounds, phenyl vinyl sulfone, and acrylonitrile was studied in detail. The cyclization smoothly proceeded to afford 4-dimethylamino-1,4,5,6-tetrahydropyrimidines or 1,6-dihydropyrimidines in good yields. The isolated 4-dimethylamino-1,4,5,6-tetrahydropyrimidines were converted to 2,5-disubstituted-1,6-dihydropyrimidines through the β-elimination of the dimethylamino group. 2,5-Disubstituted-1,4(6)-dihydropyrimidines were obtained after removal of the N-Boc or N-Cbz group. Independent tautomers of the resulting dihydropyrimidines were observed.     

Low-cost and multi-gram scale synthesis of chiral Nβ-Boc protected α-Nα-hydrazino diesters

An efficient and general low-cost method is described to obtain chiral N^β-Boc protected α-N^α-hydrazino diester building-blocks (orthogonally and non-orthogonally protected diesters) on multi-gram scale (30 mmol) using two successive S_N2 reactions. This method is also convenient for the introduction of both polar and nonpolar side chains on the N^α-atom and represents an inexpensive and attractive alternative compared to the more expensive method using commercial oxaziridine reagents for N-amination of α-amino acids.     

Use of Stille-type cross-coupling as a route to oligopyridylimines

The new tin reagents, 2-(n-Bu₃Sn)-6-{C(R)OCH₂CH₂O}-C₅H₃N, (R=H a, Me b), have been employed in Stille-type cross-coupling reactions with a range of oligopyridylbromides generating, following a facile deprotection step, a series of formyl- and acetyl-functionalised oligopyridines. Condensation reactions with 2,6-diisopropylaniline has allowed access to families of novel sterically bulky multidentate N,N,N,N (tetradentate), N,N,N,N,N (pentadentate), N,N,N,N,N,N (sexidentate) and N,N,N,N,N,N,N (heptadentate) nitrogen donor ligands. This work represents a straightforward and rapid synthetic route for the preparation of oligopyridylimines, which are expected to act as useful components for the self-assembly of polymetallic complexes.     

Facile direct synthesis of unsymmetrical ureas from N-Alloc-, N-Cbz-, and N-Boc-protected amines using DABAL-Me3

A practical synthetic method for the direct synthesis of unsymmetrically substituted ureas from N-Alloc-, N-Cbz-, and N-Boc-protected amines is described. In this study, efficient direct conversion of the Alloc-, Cbz-, and Boc-carbamate compounds to ureas was achieved in the presence of DABAL-Me₃, an air stable and easily handled reagent. Using this reaction method, both protected aromatic and aliphatic amines were successfully transformed into various trisubstituted and tetrasubstituted ureas with high yields without side product. Our findings offer promising guidelines for direct preparation of useful ureas from N-Alloc-, N-Cbz-, and N-Boc-carbamates.     

One-pot synthesis of imidazolines from aldehydes: detailed study about solvents and substrates

Imidazolines were prepared in one-pot operation from aldehydes and diamines through oxidation of aminal intermediates by NBS. This method could be applied to various aromatic and aliphatic aldehydes and N-nonsubstituted and N-monosubstituted 1,2-diamines. Furthermore, it was found that CH₂Cl₂ could be altered to TBME, a more environmentally friendly solvent, in the reaction using N-nonsubstituted 1,2-diamines. The reaction conditions were very mild and chemoselective.     

4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane N,N′-dioxide tetrahydrate: Synthesis and crystal structure

N,N′-Substituted 2.2.2-cryptand, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane N,N′-dioxide, is synthesized by an unusual method. The X-ray diffraction crystal structure of its tetrahydrate (C₁₈H₃₆N₂O₈) · 4H₂O is studied (space group P $\bar 1$ , a = 8.040 Å, b = 11.883 Å, c = 14.451 Å, α = 65.78°, β = 81.10°, γ = 89.12°, Z = 2) by a direct method and refined by the least-squares method in the anisotropic approximation (R = 0.069 for 3244 independent reflections, CAD4 automated diffractometer, λMoK _α radiation). The macrocyclic molecule has exo-exo conformation with the two O atoms at the N atoms directed outside its cavity. A crystal of compound I contains hydrogen bonds formed by all H atoms of all water molecules; these H-bonds link the water molecule into zigzag-like complicated infinite chains.     

An N-protection free ligation of the peptide thioester and the peptide with an N-alkoxy- or N-aryloxyamino group at its N-terminus

Peptides with an N-alkoxy or N-aryloxy amino acid at their N-terminus were synthesized and successfully ligated with a peptide thioester by silver ion activation under a slightly acidic condition without requiring protection of the side chain amino groups. The N-methoxy group was easily cleaved by the SmI₂ reduction in CH₃OH aq. to obtain the desired peptide with a native peptide bond. This method was successfully applied to the synthesis of the human atrial natriuretic peptide showing the efficiency of the novel ligation.     

Constructing a coplanar heterojunction through enhanced π-π conjugation in g-C3N4 for efficient solar-driven water splitting

Adjusting the electronic structure of graphitic carbon nitride（g-C₃N₄） photocatalyst through π-π conjugation is an effective method to achieve efficient photogenerated carrier separation. One key challenge ofπ-π conjugation control is to tune the degree of such conjugation without destroying the g-C₃N₄structure. Herein we report a conceptual design that achieves a coplanar heterojunction by enhancing theπ-π conjugation via the doping of crystalline g-C...     

Preparation, structure and photoluminescence properties of Eu and Ce-doped SrYSi4N7

Undoped and Eu²⁺ or Ce³⁺-doped SrYSi₄N₇ were synthesized by solid-state reaction method at 1400-1660 °C under nitrogen/hydrogen atmosphere. The crystal structure was refined from the X-ray powder diffraction data by the Rietveld method. SrYSi₄N₇ and EuYSi₄N₇, being isotypic with the family of compounds MYbSi₄N₇ (M=Sr, Eu, Ba) and BaYSi₄N_7, crystallize with the hexagonal symmetry: space group P6₃mc (No. 186), Z=2, a=6.0160 (1) Å, c=9.7894 (1) Å, V=306.83(3) Å³; and a=6.0123 (1) Å, c=9.7869 (1) Å, V=306.37(1) Å³, respectively. Photoluminescence properties have been studied for Sr_1−xEu_xYSi₄N₇ (x=0-1) and SrY_1−xCe_xSi₄N₇ (x=0-0.03) at room temperature. Eu²⁺-doped SrYSi₄N₇ shows a broad yellow emission band peaking around 548-570 nm, while Ce³⁺-doped SrYSi₄N₇ exhibits a blue emission band with a maximum at about 450 nm. SrYSi₄N₇:Eu²⁺ can be very well excited by 390 nm radiation, which makes this material attractive as conversion phosphor for LED lighting applications.     

A convenient method for the synthesis of N-hydroxyureas

Treatment of amines with 1-(4-nitrophenol)-N-(O-benzylhydroxy)carbamate yields the O-benzyl protected N-hydroxyureas. Hydrogenation of the O-benzyl protected N-hydroxyureas over 5% Pd/BaSO₄ cleanly gives the N-hydroxyureas in good yield. In addition to primary and secondary aliphatic and aromatic amines, this method converts amino sugars to the corresponding N-hydroxyureas without extensive protecting group chemistry.     

Influence of fuel-to-oxidizer ratio on the magnetic properties of Fe-doped In2O3 nanoparticles synthesized by solution combustion method

Two series of (In_1−xFe_x)₂O₃ were prepared by a solution combustion method using different fuel-to-oxidizer (i.e. glycine/metal nitrate, G/N) ratios. The crystal structure and magnetic properties of the compounds were investigated by means of X-ray diffraction, transmission electron microscopy and magnetic measurements. Detailed structural analysis shows the solubility limits of Fe in In₂O₃ are x=0.08 and 0.45 for the G/N ratios of 5/4 and 5/6, respectively. Crystallite size of the samples prepared with the G/N ratio of 5/6 is much smaller than that of the samples prepared with the G/N ratio of 5/4. At room temperature, the sample with x=0.01 prepared with the G/N ratio of 5/4 is paramagnetic and those with x=0.03-0.07 are ferromagnetic, whereas the samples with x=0.15-0.45 prepared with the G/N ratio of 5/6 show superparamagnetic behavior and those samples with x<0.15 are paramagnetic. Different magnetic behavior of these two series of samples could be attributed to different origins of magnetism. The magnetism of the samples prepared with the G/N ratio of 5/4 might originate from the existence of mixed valence Fe ions whereas the magnetism of the samples prepared with the G/N ratio of 5/6 could be due to the small crystallite size.     

The interfacial electrochemistry of goethite (α-FeOOH) especially the effect of CO2 contamination

The surface charge density/pH function of goethite is shown to be very similar to the surface charge density/surface potential functions reported for mercury. This finding differs from all other reports and we attribute the difference to the experimental method. This paper describes a method of titrating oxide suspensions which reduces pH drifts and suspension and stirring effects to negligible values and also a method for effectively removing CO₂ from oxide suspensions. When goethite which had been stored as a suspension in contact with air was titrated in N₂-purged NaI solution the point of zero charge (pzc) was within the range found by previous workers, i.e. pH 8.75 and the σ/pH function did not resemble reported σ/ψ₀ functions of mercury but when goethite from the same preparation was purged with N₂ for 2 months and then titrated in N₂-purged NaI the pzc was pH 9.3 and the σ/pH function did resemble the σ/ψ₀ function of mercury.