Green chemical syntheses and applications within organophosphorus chemistry

Application of the microwave (MW) technique offers many advantages in organophosphorus syntheses. Reluctant reactions may take place on MW irradiation. In most cases, MWs make the reactions more efficient in respect of rate, selectivity and yield. The benefits are shown via representative examples. MW irradiation may replace a catalyst, or simplify catalytic systems. The synthesis of catalysts incorporating heterocyclic P-ligands is also discussed. Where it was relevant, structural chemical details were also provided.     

Influence of rheological additives on char formation and fire resistance of intumescent coatings

Styrene-butyl acrylate copolymer based fire retardant coatings were prepared using intumescent flame-retardant additives and mineral clay type rheological additives. Three different widely used nanoclays, organic-modified montmorillonite, palygorskite and sepiolite were applied in order to determine their effect on the flame retardancy. Significant differences were found when their heat-shielding activities were evaluated. It was observed that the addition of different clay particles in amount of 0.25 w% changes the char formation process; the height, the morphology, the structure and also the mechanical resistance of the protecting shield. The different geometry and composition of the additives induced different changes in fire performance. In case of palygorskite the catalytic effect of Fe accelerated mainly the thermal decomposition, therefore the fire resistance decreased. The plate-like montmorillonite reduced the extent of the intumescent char, whereas also improved the mechanical and sustained heat resistance of the fire protecting shield. The fibrous sepiolite of low Fe content assisted the development of efficient protecting shield, which exhibited optimal cell structure, suitable thickness, and thus ensured better heat-insulating performance. Consequently, fire retardant effect of sepiolite was found to be better than the other studied clay types.     

Irreducibility criteria of Schur-type and Pólya-type

Let \({f(x)=(x-a_1)\cdots (x-a_m)}\), where a ₁, . . . , a _m are distinct rational integers. In 1908 Schur raised the question whether f(x) ± 1 is irreducible over the rationals. One year later he asked whether \({(f(x))^{2^k}+1}\) is irreducible for every k ≥ 1. In 1919 Pólya proved that if \({P(x)\in\mathbb{Z}[x]}\) is of degree m and there are m rational integer values a for which 0 < |P(a)| < 2^?N N! where \({N=\lceil m/2\rceil}\), then P(x) is irreducible. A great number of authors have published results of Schur-type or Pólya-type afterwards. Our paper contains various extensions, generalizations and improvements of results from the literature. To indicate some of them, in Theorem 3.1 a Pólya-type result is established when the ground ring is the ring of integers of an arbitrary imaginary quadratic number field. In Theorem 4.1 we describe the form of the factors of polynomials of the shape h(x) f(x) + c, where h(x) is a polynomial and c is a constant such that |c| is small with respect to the degree of h(x) f(x). We obtain irreducibility results for polynomials of the form g(f(x)) where g(x) is a monic irreducible polynomial of degree ≤ 3 or of CM-type. Besides elementary arguments we apply methods and results from algebraic number theory, interpolation theory and diophantine approximation.     

The first case of competitive heterogeneously catalyzed enantioselective hydrogenation of ketones

In competitive racemic hydrogenation of methyl benzoylformate (MBF) + ethyl pyruvate (EP) binary mixture over Pt/Al(2)O(3): k(MBF) > k(EP), but in competitive enantioselective hydrogenation k(MBF) < k(EP); the phenomenon verified for the first time is dependent on the adsorption strength of the surface complexes of various compositions (MBF-Pt, EP-Pt, MBF-CD-Pt, EP-CD-Pt, CD = cinchonidine).     

Utilization of IR spectral detailed analysis for coordination mode determination in novel Zn-cyclen-aminoacid complexes

The infrared spectra, elemental and thermal (TG/DTG and DTA) analyses of novel [Zn(cyclen-κ4N1,4,7,10)(HGly-κ2O,O')](ClO4)2 (1), and [Zn2(cyclen-κ4N1,4,7,10)2(μ-S-Ala-κ2N,O)](ClO4)(3)·2H2O (2) complexes (cyclen - 1,4,7,10-tetraazacyclododecane) were recorded and analyzed in the relation to their structural peculiarities. IR spectral data indicate both mono- or bidentate coordination mode of a carboxylate group in the prepared complexes (at pH≈9). The results indicate unusual bidentate carboxylate coordination mode (in complex (1)) toward to Zn2+-cyclen unit. Therefore the crystal structure determination of the crystalline complex [Zn(cyclen-κ4N1,4,7,10)(NO3-κ2O,O')](NO3) was attached in order to support the coordination mode assignment in complex (1).     

Composition depth profile analysis of electrodeposited alloys and metal multilayers: the reverse approach

The reverse depth profile analysis is a recently developed method for the study of a deposit composition profile in the near-substrate zone. The sample preparation technique enables one to separate the deposit and a thin cover layer from its substrate, and the initial roughness of the sample is much smaller than in the conventional sputtering direction. This technique is particularly suitable to study the zones being formed in the early phase of the electrodeposition of alloys. It has been demonstrated with the reverse depth profile analysis that in many cases when one component of an alloy is preferentially deposited, an initial zone is formed that is rich in the preferentially deposited component. This phenomenon is demonstrated for Ni–Cd, Ni–Sn, Fe–Co–Ni, Co–Ni, and Co–Ni–Cu alloys. The composition change is confined to the initial 150-nm-thick deposit, and it is the result of the interplay of the deposition preference and the depletion of the electrolyte near the cathode with respect to the ion reduced preferentially. The reverse depth profile analysis made it possible to compare the measured and the calculated composition depth profile of electrodeposited multilayers. It has been shown that the decay in the composition oscillation intensity in Co/Cu multilayers with the increase of the sputtering depth can be derived from the roughness measured as a function of the deposit thickness.     

Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid

The vibrational circular dichroism (VCD) spectrum of S-(-) and R-(+)-2-chloropropionic acid is thoroughly analyzed. Besides the VCD spectrum of the monomer, the dimers (stabilized by strong hydrogen bonds) and the 2-chloropropionic acid-CHCl(3) complexes (stabilized by a weak hydrogen bond) are studied both experimentally (in solution and in low-temperature Ar matrix) and by quantum chemical computations. It is shown that dimer formation drastically changes, and even weak complex formation can also substantially affect the overall shape of the VCD spectrum. The present and previous results can be generalized for the practice of absolute configuration determination of carboxylic acids by VCD spectroscopy. For these measurements, if bulky groups do not block dimer formation, comparison of the computed spectra of the dimers with the experimental spectra recorded in relatively concentrated (～0.1 mol dm(-3)) solutions is suggested. Our study also shows that due to the stabilization of monomers and/or the formation of weak complexes, the VCD spectrum recorded in CHCl(3) is more complex and, like in the present case, can have a lower intensity than that of the spectrum recorded in CCl(4). Therefore, if solubility allows, CCl(4) is a much preferred solvent over CHCl(3).     

Traditional uses of medicinal plants for respiratory diseases in Transylvania

Inhabitants of some Transylvanian farms in Romania have a valuable archaic knowledge of medicinal plants because of their isolation and the insufficiency of official medical treatment. In this work we present ethnobotanical data about the use of medicinal plant taxa for various respiratory diseases in the villages L?véte and Nagybacon. Altogether 34 plant taxa were documented in L?véte and 26 species in Nagybacon with 15 concordant data of the villages. This information plays an important role in the documentation of the disappearing indigenous medical information of the villages.     

A new heuristic and an exact approach for a production planning problem

Central European Journal of Operations Research - We deal with a very complex and hard scheduling problem. Two types of products are processed by a heterogeneous resource set, where resources have...