Synthesis and structural characterization of lanthanide(III) nitrate complexes of a tetraiminodiphenol macrocycle in the solid state and in solution

The lanthanide(III) complexes [Ln(LH2)(NO3)3] 1-11(La-Er), 15(Y) and [Ln(LH2)(NO3)2(H2O)](NO3) 12-14 (Tm-Lu) of the tetraiminodiphenolate macrocycle L2- have been prepared by the transmetallation reaction between [Pb(LH2)(NO3)2] and Ln(NO3)3.nH2O. In these compounds, the uncoordinated imino nitrogens are protonated and are hydrogen bonded to the phenolate oxygens. The X-ray crystal structures of the La (1), Ho (10) and Lu (14) compounds have been determined. Compounds 1 and 10, in which all the three nitrates are bound in bidentate fashion, are isostructural with distorted bicapped square antiprism geometry for the metal centre. In [Lu(LH2)(NO3)2(H2O)](NO3) 14, of the two metal bound nitrates one is bidentate and the other is unidentate, while the metal centre obtains a distorted square antiprism coordination environment. Proton NMR spectra of the paramagnetic lanthanide complexes have been studied in detail. Contributions of contact and pseudo-contact shifts to the lanthanide induced isotropic shifts (LIS) of the macrocycle protons have been separated and good agreement has been obtained between the calculated LIS values and the experimentally observed values. Analysis of the NMR data has led us to conclude that all the complexes in dimethyl sulfoxide solution attain similar configurations. The absorption and emission spectral characteristic of several compounds have been investigated. The complexes of samarium (5) and europium (6) on photoexcitation at 400 nm exhibit well-resolved luminescence spectra at 77 K both in the solid state and a methanol-ethanol (1 : 4) glassy matrix. For the terbium (8) and dysprosium (9) complexes, however, the observed luminescence peaks are less resolved and weak in intensity.     

Unraveling the nature of the segmentation clock: Intrinsic disorder of clock proteins and their interaction map

Vertebrate segmentation has been proved to be under a strict temporal control governed by a biological clock, known as the segmentation clock. The present experimental evidence suggests that the segmentation clock initiates and maintains its periodic cycle by the periodic activation or inhibition of the Notch signaling pathway as well as the periodic autoregulation of the cyclic genes themselves. In this paper, we investigate the structural and evolutionary properties of the Notch pathway proteins involved in the mice segmentation clock and computationally identify the interaction map within the Notch signaling pathway. The results of our analysis strongly indicate that most of the pathway proteins are intrinsically disordered and that the mechanism of their interaction likely involves helical molecular recognition elements, short loosely structured segments within disordered regions which are directly involved in protein-protein interactions. Predicted interactions are in agreement with gene knock-out studies available in the literature.     

Elastic wave propagation in sinusoidally corrugated waveguides

The ultrasonic wave propagation in sinusoidally corrugated waveguides is studied in this paper. Periodically corrugated waveguides are gaining popularity in the field of vibration control and for designing structures with desired acoustic band gaps. Currently only numerical method (Boundary Element Method or Finite Element Method) based packages (e.g., PZFlex) are in principle capable of modeling ultrasonic fields in complex structures with rapid change of curvatures at the interfaces and boundaries but no analyses have been reported. However, the packages are very CPU intensive; it requires a huge amount of computation memory and time for its execution. In this paper a new semi-analytical technique called Distributed Point Source Method (DPSM) is used to model the ultrasonic field in sinusoidally corrugated waveguides immersed in water where the interface curvature changes rapidly. DPSM results are compared with analytical solutions. It is found that when a narrow ultrasonic beam hits the corrugation peaks at an angle, the wave propagates in the backward direction in waveguides with high corrugation depth. However, in waveguides with small corrugation the wave propagates in the forward direction. The forward and backward propagation phenomenon is found to be independent of the signal frequency and depends on the degree of corrugation.     

Fabrication of magnetically separable palladium–graphene nanocomposite with unique catalytic property of hydrogenation

One step solvothermal route has been developed to prepare a well dispersed magnetically separable palladium–graphene nanocomposite, which can act as a unique catalyst against hydrogenation due to the uniform decoration of palladium nanoparticles throughout the surface of the magnetite–graphene nanocomposite and hence can be reused for several times. In addition to catalytic activity, palladium nanoparticles also facilitate the formation and homogeneous distribution of magnetite (Fe₃O₄) nanoparticles onto the graphene surfaces or else an agglomerated product has been obtained after the solvothermal reduction of graphene oxide in presence of Fe³⁺ alone.     

Cyclo- and carbophosphazene-supported ligands for the assembly of heterometallic (Cu2+/Ca2+, Cu2+/Dy3+, Cu2+/Tb3+) complexes: synthesis, structure, and magnetism

The carbophosphazene and cyclophosphazene hydrazides, [{NC(N(CH(3))(2))}(2){NP{N(CH(3))NH(2)}(2)}] (1) and [N(3)P(3)(O(2)C(12)H(8))(2){N(CH(3))NH(2)}(2)] were condensed with o-vanillin to afford the multisite coordination ligands [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-OH)(m-OCH(3))}(2)}] (2) and [{N(2)P(2)(O(2)C(12)H(8))(2)}{NP{N(CH(3))N═CH-C (6)H(3)-(o-OH)(m-OCH(3))}(2)}] (3), respectively. These ligands were used for the preparation of heterometallic complexes [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuCa(NO(3))(2)}] (4), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{Cu(2)Ca(2)(NO(3))(4)}]·4H(2)O (5), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(4)}]·CH(3)COCH(3) (6), [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(3)}] (7), and [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuTb(NO(3))(3)}] (8). The molecular structures of these compounds reveals that the ligands 2 and 3 possess dual coordination pockets which are used to specifically bind the transition metal ion and the alkaline earth/lanthanide metal ion; the Cu(2+)/Ca(2+), Cu(2+)/Tb(3+), and Cu(2+)/Dy(3+) pairs in these compounds are brought together by phenoxide and methoxy oxygen atoms. While 4, 6, 7, and 8 are dinuclear complexes, 5 is a tetranuclear complex. Detailed magnetic properties on 6-8 reveal that these compounds show weak couplings between the magnetic centers and magnetic anisotropy. However, the ac susceptibility experiments did not reveal any out of phase signal suggesting that in these compounds slow relaxation of magnetization is absent above 1.8 K.     

Synthesis and reactivity of enediyne–nucleobase hybrids: effect of intramolecular π-stacking

Three distinct classes of nucleobase-containing enediynes 1–9 with varying nature of the linker have been synthesized to explore the effect of π-stacking interaction in accelerating the rate of Bergman cyclization (BC). Chemical reactivity study, both experimental and computations demonstrated the important role that aromatic π-stacking interactions between the appended nucleobases within an enediyne frame play in lowering the activation barrier of Bergman cyclization.     

Phase Transitions in Gravitational Allocation

Given a Poisson point process of unit masses (“stars”) in dimension d ≥ 3, Newtonian gravity partitions space into domains of attraction (cells) of equal volume. In earlier work, we showed the diameters of these cells have exponential tails. Here we analyze the quantitative geometry of the cells and show that their large deviations occur at the stretched-exponential scale. More precisely, the probability that mass exp(−R ^γ ) in a cell travels distance R decays like exp(-R^f_d(g)){\left(-R^{f_d(\gamma)}\right)} where we identify the functions f _d (·) exactly. These functions are piecewise smooth and the discontinuities of f^￠_d{f^{\prime}_d} represent phase transitions. In dimension d = 3, the large deviation is due to a “distant attracting galaxy” but a phase transition occurs when f ₃(γ) = 1 (at that point, the fluctuations due to individual stars dominate). When d ≥ 5, the large deviation is due to a thin tube (a “wormhole”) along which the star density increases monotonically, until the point f _d (γ) = 1 (where again fluctuations due to individual stars dominate). In dimension 4 we find a double phase transition, where the transition between low-dimensional behavior (attracting galaxy) and highdimensional behavior (wormhole) occurs at γ = 4/3.     

The baryon loop tension from continuum QCD

The energy of three static widely separated quarks in a colour singlet state is computed by studying the large area behaviour of different baryon loops in continuum QCD. With the help of a sum rule like approach the corresponding string tensions are obtained in terms of the vacuum condensates. They can be interpreted as due to effective quark-quark forces of half the strength of the quark-antiquark forces, at least.     

Thiosteroids in sewage sludge and its post-treatment products

Different sulphur compound derivatives from steroids were detected and quantified in the analysis of the lipidic fraction of sewage sludge and its post-treatment products, including thermally dried sludge and compost. Some steroid thiols: 5α-cholestane-3β-thiol, 24-methyl-5α-cholestane-3β-thiol and 24-ethyl-5α-cholestane-3β-thiol were detected in the gas chromatography with mass spectrometry detector (GC-MS) analysis. These three compounds, related to the thiostanol family, have only been encountered in previous studies in sea sediments. Gas chromatography with sulphur-selective flame photometric detector (GC-FPD) was used with the objective of detecting other related compounds in sludge. It allowed the detection of other compounds, whose mass spectra could correspond with the one of the steroid enethiols. The research focused on detecting the formation point of these sulphur compounds in the sludge treatment process, as well as their biodegradation resistance in the post-treatment processes. The amount of these products in the sludge was quantified using gas chromatography with flame ionization detector (GC-FID). The result of this study confirms that the identified compounds are not easily biodegradable.     

Kinetics and mechanism of solvent extraction of copper with kelex 100 in presence of nitrilotriacetic acid

A detailed study of the extraction kinetic behavior of copper(II) in aqueous media containing nitrilotriacetic acid (H₃Y) into chloroform solutions of Kelex 100, a high-molecular-weight alkylated 8-quinolinol, is described. The rate expression for the extraction of copper by Kelex 100, described by the expression —d[Cu²⁺]/dt = k' [Cu²⁺][HL]_o/ [HY^2-]^0.5, supports a mechanism in which the rate-determining steps are the concurrent reactions of Cu²⁺ and CuY^- with a neutral Kelex 100 molecule in the aqueous phase.