Coordination preference and magnetic properties of FeII assemblies with a bis-azole bearing 1,2,4-triazole and tetrazole

With a new bis-azole molecular fragment (Htt) bearing 1,2,4-triazole and tetrazole, a mononuclear complex [Fe(tt)₂(H₂O)₄]·2H₂O (1), a trinuclear complex [Fe₃(tt)₆(H₂O)₆]·2H₂O (2) and a 1D coordination polymer [Fe(tt)(Htt)₂]BF₄·2CH₃OH (3) were obtained by varying reaction conditions. Htt acts either as an anionic or neutral ligand depending upon the reaction medium and pH. Thermal variation of spin states of 1–3 were investigated in the range 77–300?K by ⁵⁷Fe M?ssbauer spectroscopy. 1 totally remains in high-spin state over the entire temperature range whereas no spin crossover was evidenced in 2. Nearly 1:1 high-spin and low-spin population ratio is found in 3, which remains constant over the entire temperature range investigated.     

Nuclear magnetic resonance in noncollinear antiferromagnet Mn3Al2Ge3O12

The ⁵⁵Mn nuclear magnetic resonance spectrum of noncollinear 12-sublattice antiferromagnet Mn₃Al₂Ge₃O₁₂ has been studied in the frequency range of 200–640 MHz in the external magnetic field H ‖ [001] at T = 1.2 K. Three absorption lines have been observed in fields less than the field of the reorientation transition H _c at the polarization h ‖ H of the rf field. Two lines have been observed at H > H _c and h ⊥ H. The spectral parameters indicate that the magnetic structure of manganese garnet differs slightly from the exchange triangular 120-degree structure. The anisotropy of the spin reduction and (or) weak antiferromagnetism that are allowed by the crystal symmetry lead to the difference of ≈3% in the magnetization of sublattices in the field H < H _c. When the spin plane rotates from the orientation perpendicular to the C ₃ axis to the orientation perpendicular to the C ₄ axis, all magnetic moments of the electronic subsystem decrease by ≈2% from the average value in the zero field.     

Hyperfine structure investigations of some odd levels of Co I by level crossing and optical methods

Using the level crossing technique the ratios and absolute values of the hyperfine structure (hfs) constants of the levelsz ⁴F_9/2 andz ⁴F_7/2 of the configuration 3d ⁷4s4p of Co I were measured:z ⁴ F _9/2: ¦A¦=(811±12)MHz; ¦B¦=(48±93) MHz;B/A=?0.06±0.11 A>0; B<0z ⁴ F _7/2: ¦A¦ = (659 ±11)MHz; ¦B¦=(33±84)MHz;B/A=?0.05±0.13 A>0; B<0. In addition the hfs constants of three other excited levels of Co I could be determined by optical methods:z ⁴ F _9/2:A=525±26 MHz;B=200 MHzy ⁴ F _9/2:A=300±30 MHz;B=?500 MHzy ⁴ G _11/2:A=315±20 MHz;B=400 MHz. The experimental results are compared with known experimental and also with theoretical values which where calculated using the parametric potential method.     

Synthesis and Study the Effect of Donor-Acceptor Substituent on Fluorescence Behavior of Thieno[3, 2-c]pyridine Derivatives

4-Hetero-1-yl-2-bromothieno[3,2-c]pyridines 3(a–d) were synthesized by the reaction of 2-bromo-4-chlorothieno[3,2-c]pyridine (1) and cyclic amine 2(a–d), which on Suzuki coupling with substituted boronic acids 4(a–f) exclusively converted to corresponding 4-hetero -1-yl-2-arylthieno[3,2-c]pyridine 5(a–x) in good yields. The effect of donor-acceptor substituent on absorption emission properties and fluorescent quantum yield of new thienopyridine derivatives 5(a-x) were studied.     

Combretastatin A-4 derivatives: synthesis and evaluation of 2,4,5-triaryl-1H-imidazoles as potential agents against H1299 (non-small cell lung cancer cell)

A number of 2,4,5-triaryl-1H-imidazole derivatives were synthesized and evaluated for their antiproliferative activities against the growth of five cell lines including three non-small cell lung cancers (H460, H1299, and A549), one breast cancer (MCF-7), and one normal diploid embryonic lung cell line (MRC-5). Preliminary results indicated that both 2-(5-bromofuran-2-yl)-4,5-bis{4-[3-(dimethylamino) propoxy] phenyl}-1H-imidazole (10f) and 4,5-bis{4-[3-(dimethylamino)propoxy]phenyl}-2-(5-nitrofuran-2-yl)-1H -imidazole (10g) were selectively active against the growth of H1229 with an IC₅₀ of less than 0.1???M, thus were more active than topotecan (IC₅₀ >?10.0??? M). However, both 10f and 10g exhibited only marginal cytotoxicity against H460, A549, MCF-7, and MRC-5 requiring an IC ₅₀ of at least 4.16???M. Our results also indicated that 10f induced H1299 cell cycle arrest at G0/G1 through the inactivation of p38 MAPK, JNK, ERK, as well as the expression of SIRT1 and survivin. These results suggested that 10f might have therapeutic potential against H1299 (non-small cell lung cancer cell).     

Aging effect in CaLaBa{Cu1???xFex}3O7???�� with 0 �� x �� 0.07 studied by M?ssbauer spectroscopy

In this work, we study the long-term aging effect caused by Fe atoms in the superconductor CaLaBa{Cu_1???xFe_x}₃O_7????? with 0 ?? x ?? 0.07. XRD confirms that this system has a YBCO-like structure. The critical temperature (T_c) is strongly affected by aging and depends on the amount of Fe in the structure. Room temperature Mössbauer spectroscopy reveals the presence of the typical species A, B?CB ??, C and new species E ?? and F. Interestingly; A, which corresponds to the Fe^3?+? atom located in the Cu(1) of the chains with spin S _z = 3/2, shows a drastic reduction which means migration to the species B, B ?? and C. Species B and B ?? correspond to the Fe^3?+? in the Cu(2) site forming planar quasi-octahedral and planar square pyramidal, while the C specie is a square pyramidal with O(5) respectively (spin S_z = 3/2 in all these cases). Aging causes loss of superconductivity in the samples with 5 and 7% of iron content.     

Phase diagram of antiferromagnetic cobalt fluoride

The H-T phase diagram of antiferromagnetic cobalt fluoride in an external magnetic field H perpendicular to the easy magnetization axis A is completed and used to construct a phase diagram in the variables H _z and H _y . In this diagram, the lines corresponding to second-order phase transitions (between an angular phase and a phase with antiferromagnetic vector I ⊥ A) begin and end in fields of a spin-flip transition (i.e., in an exchange field). A peculiarity of these lines of phase transitions is that each of them has two tricritical points at which this line of second-order phase transitions transforms into a line of first-order phase transitions. A critical angle between the direction of the external magnetic field and the basal plane within which the first-order phase transition takes place is determined.     

Modeling of the molecular and electronic structures of multiple-decker sandwich macromolecules with η5-π bonds on the basis of biscyclopentadienyl derivatives 60H10 of a C60 fullerene

The molecular and electronic structures of the (CpFe)₂C₆₀H₁₀ complex of the D _5d symmetry, where Cp is the $^ \cdot C_5 H_5 $ cyclopentadienyl radical, are simulated using the ab initio Hartree-Fock-Roothaan method in the 3–21G basis set. In this complex, hydrogen atoms are attached to carbon atoms of the C₆₀ fullerene which occupy α-positions with respect to two oppositely lying five-membered rings. Each FeCp semisandwich moiety is linked to atoms of one of these five-membered rings by the η⁵-π-type bond. It is found that the energy of the η⁵-π Fe-C₆₀H₁₀ bonds in the (CpFe)₂C₆₀H₁₀ complex is comparable to that of the η⁵-π Fe-Cp bond in the FeCp₂ ferrocene molecule. The optimum geometry calculated for the (CpFe)₂C₆₀H₁₀ complex is used for modeling of the structure of the quasi-linear macromolecule [-FeC₆₀H₁₀-]_n, (I). The band structure of the energy spectrum of macromolecule I is calculated in the valence approximation of the extended Hückel method within the crystalline-orbital approach. The band gap in the spectrum of macromolecule I is ～2.27 eV. The band structure of the spectrum of this macromolecule is compared with the spectra of the hypothetical molecules [-FeCp-]_n and [-FeC₂₀-]_n.     

Phosphorus(V)corrole- Porphyrin Based Hetero Trimers: Synthesis,Spectroscopy and Photochemistry

‘Axial-bonding’-type hetero trimers have been constructed by employing a simple ‘inorganic’ reaction such as axial bond formation of main group element containing phosphorus corrole. The approach is simple and modular in nature. The architecture of these hetero trimers such that, while a phosphorus(V)corrole forms the basal scaffolding unit, either two free-base porphyrins [(H ₂ ) ₂ –PCor] or Zn^II porphyrins [(Zn) ₂ –PCor] occupy the two axial sites via an aryloxy bridge. Both hetero trimeric species have been completely characterized by mass (FAB), UV/Vis, proton nuclear magnetic resonance spectroscopies and also by the differential pulse voltammetric method. Comparison of their spectroscopic and electrochemical data of these trimers with those of the corresponding reference compounds reveal that there is no apparent ring-to-ring interactions in these ‘vertically’ linked hetero trimers. Reduced fluorescence quantum yields were observed for [(H ₂ ) ₂ –PCor] and [(Zn) ₂ –PCor] when compared to corresponding monomeric chromophores. Finally, a comparison is made between the presently reported phosphorus(V)corrole based hetero arrays and the previously reported analogous arrays based on Ge(IV)corrole with regard to their spectroscopic properties and photochemical activities.     

Many-atom interactions in the theory of higher order elastic moduli: A general theory

The total potential energy of a crystal U({r _ik }) as a function of the vectors r _ik connecting centers of equilibrium positions of the ith and kth atoms is assumed to be represented as a sum of irreducible interaction energies in clusters containing pairs, triples, and quadruples of atoms located in sites of the crystal lattice A2: U({r _ik }) ≡ Σ _N=1 ⁴ E _N ({r _ik }). The curly brackets denote the “entire set.” A complete set of invariants {I _j ({r _ik })} _N , which determine the energy of each individual cluster as a function of the vectors connecting centers of equilibrium positions of atoms in the cluster E _N ({r _ik }) ≡ E _N ({I _j ({r _ik })} _N ), is obtained from symmetry considerations. The vectors r _ik are represented in the form of an expansion in the basis of the Bravais lattice. This makes it possible to represent the invariants {I _j ({r _ik })} _N in the form of polynomials of integers multiplied by τ ₂ ^m . Here, τ₂ is one-half of the edge of the unit cell in the A2 structure and m is a constant determined by the model of interaction energy in pairs, triples, and quadruples of atoms. The model interaction potential between atoms in the form of a sum of the Lennard-Jones interaction potential and similarly constructed interaction potentials of triples and quadruples of atoms is considered as an example. Within this model, analytical expressions for second-order and third-order elastic moduli of crystals with the A2 structure are obtained.     

Rotation of the plane of polarization and linear birefringence of sound in hematite below the morin point

The linear antiferromagnetic birefringence of sound in hematite (α-Fe₂O₃) residing in the collinear easy-axis phase (L ‖ C ₃) below the Morin point is experimentally studied. The plane of polarization of a linearly polarized transverse acoustic wave propagating along the trigonal axis C ₃ of a hematite crystal placed in a magnetic field H applied in the basal plane (H ⊥ C ₃, 3.5 ≤ H ≤ 15 kOe) is found to rotate after a temperature-driven orientational phase transition to the easy-axis state. The angle of rotation exhibits a 180° angular dependence on the direction of the magnetic field in the basal plane and varies from zero to ～π/2. Numerical estimates suggest that the conditions necessary for rotation of the plane of polarization through appreciable angles (～π/2) can be satisfied in the easy-axis phase at orientational phase transition temperatures close to the Morin point, which actually takes place in the fields employed. The results obtained are described sufficiently well by the theory of linear antiferromagnetic birefringence of sound (E.A. Turov) and confirm its main conclusions.     

Sonochemical Synthesis and Characterization of the Copper(II) Nanocomplex: DNA- and BSA-Binding,Cell Imaging,and Cytotoxicity Against the Human Carcinoma Cell Lines

The focus of the present work is the preparation of new metal-based nanodrug to overcome limitations of chemotherapy such as poor water solubility of most common chemotherapeutic drugs. The copper(II) complex of 1,2,4-triazine derivatives, [Cu(dppt)₂(H₂O)₂]²⁺ (dppt is 5,6-diphenyl- 3- (2-pyridyl)-1,2,4-triazine), has been synthesized at nano-size by sonochemical method and characterized by FTIR, zetasizer, and scanning electron microscopy (SEM). The interaction of the complex and nanocomplex with fish sperm DNA (FS–DNA) and BSA have been investigated under physiological conditions by a series of experimental methods. The results have indicated that the complex binds to FS–DNA by two biding modes, viz., electrostatic and intercalates into the base pairs of DNA. The competitive study with ethidium bromide (EB) shows that the complex and nanocomplex competes for the DNA–binding sites with EB. Protein binding studies show that the complex and nanocomplex could bind with BSA. The results of synchronous fluorescence of BSA show that additions of the complex affect the microenvironment of both tyrosine and tryptophan residues during the binding process. The in vitro cytotoxicity of the complex (solution in DMSO) and nanocomplex (colloid in H₂O) against the human carcinoma cell lines (MCF-7 and A-549) was evaluated by MTT assay. The results of in vitro cytotoxicity indicate that the complex and nanocomplex have excellent cytotoxicity activity against MCF-7 and A-549. Results of the microscopic analyses of the cancer cells confirm the results of the cytotoxicity.     

Urea Based Dipodal Fluorescence Receptor for Sensing of Fe3+ Ion in Semi-Aqueous Medium

Urea based fluorescent chemosensor 1 was synthesized. Receptor 1 shows unique selectivity for the Fe³⁺ion and no such significant response was noticed with other metal ions (Cr³⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺ and Bi³⁺) in DMSO/H₂O (50:50,v/v) semi-aqueous solution. The binding features have been established by absorption and fluorescence spectroscopic methods. The binding constant (K) values obtained from Benesi-Hildebrand, Scatchard and Connor plot for receptor 1 is (8.3?±?0.3) × 10³ M^?1 and has good detection limit 0.7?μM. The stoichiometry of 1.Fe³⁺ complex was confirmed by mass spectroscopy and Job’s plot.

Bis-Benzimidazolyl Diamide Based Fluorescent Probe for Copper(II): Synthesis, Structural and Fluorescence Studies

A new fluorescent probe based on a bis-benzimidazole diamide N ²,N ^2′-bis[(1-ethyl-benzimidazol-2-yl)methyl]biphenyl-2,2′-dicarboxamide ligand L ₁ with a biphenyl spacer group and a Copper(II) trinuclear metallacycle has been synthesized and characterized by X-ray single crystallography, elemental and spectral (FT-IR, ¹H & ¹³C NMR, UV-Visible) analysis. The fluorescence spectra of L ₁ in MeOH show an emission band centered at 300 nm. This band arises due to benzimidazolyl moiety in the ligating system. The diamide L ₁ in the presence of Cu²⁺ show the simultaneous ‘quenching’ of (300 nm) and ‘enhancement’ of (375 nm) emission band. Similar fluorescence behavior was found in water–methanol mixture (9:1). The new emission band at 375 nm is attributed to intra ligand π–π* transition of the biphenyl moiety. L ₁ exhibited high selectivity and sensitivity towards Cu²⁺ in both the medium over other common metal ions like Ni²⁺, Co²⁺, Mn²⁺, Mg²⁺, Zn²⁺, Pb²⁺ and Hg²⁺. The binding constant with Cu²⁺ was calculated by the Benesi-Hildebrand equation. Selective “off-on-off” behavior of L ₁ in methanol has also been studied. The fluorescent intensity of 375 nm bands in L ₁ enhances (turns-on) upon addition of Cu²⁺ and quenches (turn-off) upon addition of Na₂-EDTA.     

Structure and biological properties of sodium and potassium 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionates

Sodium (1) and potassium (2) 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionates form crystal hydrates, which exist as both monomers and dimers. Quantum-chemical calculations in the PM6 approximation are used to determined the enthalpies of formation ?H _f ^po , thermal enthalpy H ^po, and entropy S ^po of the monomers and dimers, which are indicative of the possibility of existence of the dimers of propionates of alkali metals. The biological activity of these compounds in animal and plants is demonstrated to be dependent on their concentrations. Compounds 1 and 2 turned out to be efficient in the treatment of burn injuries, cancer, and radiation damage (in vivo and in vitro), as well as in promoting the growth of cereal plants.     

Specific features of the thermal electromotive force in Bi quantum wires in transverse magnetic and electric fields

The thermal electromotive force (emf) in Bi quantum wires has been calculated in the model of potential in the form of a paraboloid of revolution in a uniform magnetic field H, which is normal to the axis of the studied nanostructure, and in a direct-current (dc) electric field E ‖ H. It has been shown that, with an increase in E, the thermal emf α _xx is described by a nonmonotonic function at different values of H. A physical interpretation of this behavior of α _xx as a function of E is proposed with account for the interaction between carriers and the rough surface of the nanowire.     

Spatial representation of groups of automorphisms of von Neumann algebras with properly infinite commutant

Theorem. Let a topological groupG be represented (a→φ _a ) by *-automorphisms of a von Neumann algebraR acting on a separable Hilbert spaceH. Suppose that

1. G is locally compact and separable,
2. R′ is properly infinite,
3. for anyT∈R,x,y∈H the function

$$a \to \left\langle {\phi _a (T)x,y} \right\rangle _H $$ is measurable onG. Then there exists a strongly continuous unitary representation ofG onH,a→U _a , such that forT∈R,a∈G, $$\phi _\alpha (T) = U_a TU_a *.$$ .     

Synthesis and Spectroscopic Properties of Novel Fluorescent Compounds Containing Bis-pyrazole Ring

A series of pyrazoline derivatives containing pyrazole group were synthesized and characterized by means of ¹H NMR, FT-IR, MS and elemental analysis, and their UV–vis absorption behavior and fluorescent properties were also measured. Moreover, the influence of metal ions on spectral properties of synthetic products was examined with compound A ₅ as an example. It has been found that all synthetic pyrazoline derivatives show two remarkable absorption peaks at about 260 and 360 nm and the maximum emission peak at 445–467 nm. Especially, the joined of Co²⁺ can quench the fluorescence of compound A ₅ obviously.