On the transitivity of multifunctions and density of orbits in generalized topological spaces

The connection between transitivity and existence of a dense orbit for multifunctions $\phi \: X\multimap X$ in generalized topological spaces is studied. Moreover strongly transitive multifunctions and functions in generalized topological spaces are investigated.     

Frequency-domain spectroscopic study of the PS I-CP43' supercomplex from the cyanobacterium Synechocystis PCC 6803 grown under iron stress conditions

Absorption, fluorescence excitation, emission, and hole-burning (HB) spectra were measured at liquid helium temperatures for the PS I-CP43' supercomplexes of Synechocystis PCC 6803 grown under iron stress conditions and for respective trimeric PS I cores. Results are compared with those of room temperature, time-domain experiments (Biochemistry 2003, 42, 3893) as well as with the low-temperature steady-state experiments on PS I-CP43' supercomplexes of Synechococcus PCC 7942 (Biochim. Biophys. Acta 2002, 1556, 265). In contrast to the CP43' of Synechococcus PCC 7942, CP43' of Synechocystis PCC 6803 possesses two low-energy states analogous to the quasidegenerate states A and B of CP43 of photosystem II (J. Phys. Chem. B 2000, 104, 11805). Energy transfer between the CP43' and the PS I core occurs, to a significant degree, through the state A, characterized with a broader site distribution function (SDF). It is demonstrated that the low temperature (T = 5 K) excitation energy transfer (EET) time between the state A of CP43' (IsiA) and the PS I core in PS I-CP43' supercomplexes from Synechocystis PCC 6803 is about 60 ps, which is significantly slower than the EET observed at room temperature. Our results are consistent with fast (< or =10 ps) energy transfer from state B to state A in CP43'. Energy absorbed by the CP43' manifold has, on average, a greater chance of being transferred to the reaction center (RC) and utilized for charge separation than energy absorbed by the PS I core antenna. This indicates that energy is likely transferred from the CP43' to the RC along a well-defined path and that the "red antenna states" of the PS I core are localized far away from that path, most likely on the B7-A32 and B37-B38 dimers in the vicinity of the PS I trimerization domain (near PsaL subunit). We argue that the A38-A39 dimer does not contribute to the red antenna region.     

EPR Studies of DOPA–Melanin Complexes with Netilmicin and Cu(II) at Temperatures in the Range of 105–300?K

The application of electron paramagnetic resonance (EPR) spectroscopy in pharmacy of melanin complexes with netilmicin and Cu(II) was presented. The continuous microwave saturation of EPR spectra of DOPA–melanin and the complexes was performed. EPR spectra were measured on an X-band (9.3?GHz) spectrometer at temperatures in the range of 105–300?K. Paramagnetic copper ions decrease the intensity of the EPR lines of melanin’s free radicals. It was found that fast spin–lattice relaxation characterizes DOPA–melanin–Cu(II) complexes. Slow spin–lattice relaxation processes exist in melanin’s paramagnetic centers of DOPA–melanin and DOPA–melanin–netilmicin, [DOPA–melanin–netilmicin]–Cu(II), [DOPA–melanin–Cu(II)]–netilmicin complexes. Spin–lattice relaxation processes are faster at higher temperatures. The homogeneous broadening of EPR lines for melanin complexes was observed. The practical consequences of differences between paramagnetic properties of melanin complexes with netilmicin and the complexes with Cu(II) were discussed.     

Influence of Open Chain and Cyclic Structure of Peptidomimetics on Antibacterial Activity in E. coli Strains

An efficient method for the synthesis of functionalized peptidomimetics via multicomponent Ugi reaction has been developed. The application of trifluoroethanol (TFE) as a reaction medium provided desired products with good yields. Further, using the developed cyclisation reaction, the obtained peptidomimetics were transformed into the cyclic analogues (diketopiperazines, DKPs). The goal of the performed studies was to revised and compare whether the structure of the obtained structurally flexible acyclic peptidomimetics and their rigid cycling analogue DKPs affect antimicrobial activity. We studied the potential of synthesized peptidomimetics, both cyclic and acyclic, as antimicrobial drugs on model E. coli bacteria strains (k12, R2–R4). The biological assays reveal that DKPs hold more potential as antimicrobial drugs compared to open chain Ugi peptidomimetics. We believe that it can be due to the rigid cyclic structure of DKPs which promotes the membrane penetration in the cell of studied pathogens. The obtained data clearly indicate the high antibiotic potential of synthesized diketopiperazine derivatives over tested antibiotics.     

Characterization of Volatile Flavor Compounds in Supercritical Fluid Separated and Identified in Gurum (Citrulluslanatus Var. colocynthoide) Seed Oil Using HSME and GC–MS

In this study, the volatile compound profiles of gurum seed oil were determined using two methods: supercritical CO₂ extraction (SFE) and the screw press process (SPP). For volatile compounds extraction and identification, headspace solid-phase micro-extraction (HS-SPME) and GC–MS were used, respectively. A total number of 56 volatile compounds were revealed and identified in oil extracted by SFE, while only 40 compounds were detected in extracted oil by SPP. Acids, aldehydes, esters, ketones, furans, and other components were present in the highest ratio in oil extracted by SFE. In contrast, alcohols and alkenes were found in the highest proportion in oil extracted by SPP. In this study, it was observed that SFE showed an increase in the amounts of volatile compounds and favorably impacted the aroma of gurum seed oil. The results reveal that different extraction methods significantly impact the volatile components of gurum seed oil, and this study can help evaluate the quality of the oil extracted from gurum seeds.     

Chemistry of the 2,3-oxaphosphabicyclo[2.2.2]octene ring system: Extrusion of metaphosphates

The 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide (or sulfide) ring system is of considerable value because it easily fragments on being heated or irradiated (254 nm) to provide three-coordinate phosphoryl species. The system is synthesized by O-insertion with peracids into a C P bond of 7-phosphanorbornene derivatives with a variety of P-substituents. With rare exception, the insertion has been found to proceed with retention of the configuration at phosphorus, as established by X-ray and NMR techniques. The thermal fragmentation that produces the metaphosphate derivatives EtO PO₂, EtO P(S)O, and Et₂N PO₂ follows first-order kinetics, and is independent of the concentration of a trapping agent for these species. Solvent effects and activation parameters join in defining a retrocycloaddition mechanism that ejects the free metaphosphate. The species Ph PO₂ can also be easily generated either thermally or photochemically. Metaphosphates have been found to attack ethereal oxygen in epoxides and oxetanes, and may undergo anchimeric participation with a properly placed methoxy group on the substituent used in the 2,3-oxaphosphabicyclo[2.2.2]octene precursor.     

Intermolecular chain transfer to polymer with chain scission: general treatment and determination of kp/ktr in L,L-lactide polymerization

A general kinetic treatment of the system with intermolecular chain transfer followed by fast reinitiation is given. It leads to the broadening of the molecular weight distribution (MWD), the number of growing chains being invariable. Thus, this system can be considered as a special case of living polymerization. A general method has been elaborated allowing the determination of the ratio of the rate constant of propagation (k_p) to the rate constant of the bimolecular transfer (k⁽²⁾_tr) from the dependence of the MWD on monomer conversion. Numerical values of k_p/k⁽²⁾_tr equal to ≈ 10² and 25 were thus determined for the polymerization of L , L -lactide (L , L -dilactide) initiated with aluminium tris(isopropoxide) trimer ({Al(OⁱPr)₃}₃) and tributyltin ethoxide (ⁿBu₃SnOEt), respectively.     

Towards periodic copolymers with flexible and mesogenic units in the main chain. Copolymerization of tetrahydrofuran with 7-oxabicyclo[2.2.1]heptane

An attempt was made to prepare periodic polymers having promesogenic units of various lengths. Due to a certain distribution within these units, copolymers of this structure should rather be called pseudoperiodic. In order to understand better the behaviour of such systems, copolymerization of tetrahydrofuran (THF — soft units) with 7-oxabicyclo[2.2.1]-heptane (BC — hard units) was studied. The kinetically and thermodynamically controllable copolymerizations were elaborated, leading to products of different distribution of the THF and BC units. The apparent reactivity ratios are dependent on the copolymerization conditions due to the reversibility of the propagations on the THF type of active species. They vary: r̄₁ from 0.09 to 2.72, r̄₂ from 0.31 to 1.57 (1 stands for BC, 2 for THF). Pseudoperiodic copolymers of the structure $\rlap{-} [\rlap{–} ({\rm BC}\rlap{-} )_x {\rm THF}\rlap{-} ]_n $, where x̄ = 1 to 4, were prepared carrying out the copolymerization above the ceiling temperature of THF.     

Thermodynamics of homogeneous equilibrium copolymerization from the point of view of the Flory-Huggins theory

A general treatment of the thermodynamics of binary copolymerization from the point of view of the Flory-Huggins theory is given. The relations allow one to determine, on the basis of experimental data, the thermodynamic parameters of copolymerization and the parameters of intercomponent interaction (χ). On the other hand, when these parameters are known, it is possible to predict, for any initial set of conditions, the equilibrium concentrations of comonomers and the equilibrium microstructure of a copolymer. The presented simulations indicate that positive values of interaction parameters increase the volume fractions of copolymer units in equilibrium with comonomers, in comparison to an analogous copolymerization system without intercomponent interactions.