Nonrelativistic Quantum Mechanics with Fundamental Environment

Spontaneous transitions between bound states of an atomic system, “Lamb Shift” of energy levels and many other phenomena in real nonrelativistic quantum systems are connected within the influence of the quantum vacuum fluctuations (fundamental environment (FE)) which are impossible to consider in the limits of standard quantum-mechanical approaches. The joint system “quantum system (QS) + FE” is described in the framework of the stochastic differential equation (SDE) of Langevin-Schr?dinger (L-Sch) type, and is defined on the extended space R ³ ⊗ R _{ξ}, where R ³ and R _{ξ} are the Euclidean and functional spaces, respectively. The density matrix for single QS in FE is defined. The entropy of QS entangled with FE is defined and investigated in detail. It is proved that as a result of interaction of QS with environment there arise structures of various topologies which are a new quantum property of the system.     

A Fast Algorithm for Wave Propagation from a Plane or a Cylindrical Surface

The newly developed Taylor-Interpolation-FFT (TI-FFT) algorithm dramatically increases the computational speeds for millimeter wave propagation from a planar (cylindrical) surface onto a “quasi-planar” (“quasi-cylindrical”) surface. Two different scenarios are considered in this article: the planar TI-FFT is for the computation of the wave propagation from a plane onto a “quasi-planar” surface and the cylindrical TI-FFT is for the computation of wave propagation from a cylindrical surface onto a “quasi-cylindrical” surface. Due to the use of the FFT, the TI-FFT algorithm has a computational complexity of O(N ² log₂  N ²) for an N × N computational grid, instead of N ⁴ for the direct integration method. The TI-FFT algorithm has a low sampling rate according to the Nyquist sampling theorem. The algorithm has accuracy down to −80 dB and it works particularly well for narrow-band fields and “quasi-planar” (“quasi-cylindrical”) surfaces.     

A Fe<Superscript>3+</Superscript>/Hg<Superscript>2+</Superscript>-Selective Anthracene-Based Fluorescent PET Sensor with Tridentate Ionophore of Amide/β-Amino Alcohol

A new anthracene-based fluorescent PET sensor 1 with a tridentate ionophore of amide/β-amino alcohol displays very good selectivity and sensitivity for Fe³⁺ (K _a = 1.6 × 10³ M⁻¹) and Hg²⁺ (K _a = 2.1 × 10³ M⁻¹) in CH₃CN–H₂O (3:7, v/v) with detection limit of 1 μM. More fluorescence enhancement was observed when 1 selectively detected Fe³⁺ or Hg²⁺ in CH₃CN and its detection limit was up to 0.03 μM.     

A Novel Hg<Superscript>2+</Superscript> Selective Ratiometric Fluorescent Chemodosimeter Based on an Intramolecular FRET Mechanism

A irreversible Hg²⁺ selective ratiometric fluorescence probe FR, a fluorescein fluorophore linked to a rhodamine B hydrazide by a thiourea spacer, was designed and synthesized. The developed probe FR exhibited great ratiometric fluorescence enhancement and remarkable yellow-magenta color change toward Hg²⁺ with excellent selectivity in aqueous acetone solution, and the ratiometric fluorescence response to Hg²⁺ was not interfered by other metal cations including Fe³⁺, Co²⁺, Ni²⁺, Cr³⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, Mg²⁺, Ba²⁺ and Mn²⁺. The linear range and the detection limit of this supposed ratiometric fluorescence method for Hg²⁺ were 0.0–10.0 × 10⁻⁶ and 5 × 10⁻⁸ M, respectively.     

A New Highly Sensitive and Selective Fluorescent Cadmium Sensor

Condensation product (L) of salicylaldehyde and semicarbazide behaves as a fluorescent sensor for Cd²⁺ ion, in 1:1 DMSO:H₂O, over Mn²⁺, Fe²⁺, Ni²⁺, Co²⁺, Cu²⁺, Pb²⁺ and Hg²⁺ ions. The emission peak of L at λ_max = 520 nm, on excitation with 420 nm wavelength photons, showed an enhancement in intensity of ca 60-fold when interacted with Cd²⁺ ion. The intensity was however found to remain unaltered when interacted with metal ions—Mn²⁺, Fe²⁺, Ni²⁺, Co²⁺, Cu²⁺, Pb²⁺ and Hg²⁺. The intensity increases by approximately 20 fold on interaction with Zn²⁺ ion. The increase in the fluorescent peak can be explained on the basis of photo induced electron transfer (PET) mechanism. A 1:1 complexation between Cd²⁺ and L with log β = 4.25 has been proved.     

Synthesis of Highly Selective Indole-Based Sensors for Mercuric Ion

Two indole-based fluorescent chemosensors 1 and 2 were prepared and investigated characteristic features with transition metal ions. Sensors 1 and 2 were selective for Hg²⁺ ion, among a series of metal ions, in aqueous ethanol (H₂O–EtOH, 1:2, v/v) with association constants of 5.74 × 10³ and 4.46 × 10³ M⁻¹ and detection limits of 7.4 and 6.8 μM, respectively. Computational results revealed that sensor 1 or 2 with Hg²⁺ ion formed 1:1 complex with a central, sandwich-coordinated Hg²⁺ ion. Computational calculations provided evidence that a sandwich-coordinated Hg²⁺ ion center was formed and the polyoxyethylene spacer acted as a scaffold for bringing functional ligands into a suitable geometry.     

Design and Synthesis of Highly Photostable Yellow–Green Emitting 1,8-Naphthalimides as Fluorescent Sensors for Metal Cations and Protons

Two highly photostable yellow–green emitting 1,8-naphthalimides 5 and 6, containing both N-linked hindered amine moiety and a secondary or tertiary cation receptor, were synthesized for the first time. Novel compounds were configured as “fluorophore–spacer–receptor” systems based on photoinduced electron transfer. Photophysical characteristics of the dyes were investigated in DMF and water/DMF (4:1, v/v) solution. The ability of the new compounds to detect cations was evaluated by the changes in their fluorescence intensity in the presence of metal ions (Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Co²⁺) and protons. The presence of metal ions and protons was found to disallow a photoinduced electron transfer leading to an enhancement in the dye fluorescence intensity. Compound 5, containing secondary amine receptor, displayed a good sensor activity towards metal ions and protons. However the sensor activity of dye 6, containing a tertiary amine receptor and a shorter hydrocarbon spacer, was substantially higher. The results obtained indicate the potential of the novel compounds as highly photostable and efficient “off–on” pH switchers and fluorescent detectors for metal ions with pronounced selectivity towards Cu²⁺ ions.     

Membrane Dipole Potential as Measured by Ratiometric 3-Hydroxyflavone Fluorescence Probes: Accounting for Hydration Effects

We previously applied the electrochromic modulation of excited-state intramolecular proton-transfer (ESIPT) reaction for the design of novel 3-hydroxyflavone (3-HF) derivatives as fluorescent probes for measuring the dipole potential, Ψ_D, in lipid bilayers (Klymchenko et al., Proc. Natl. Acad. Sci. USA, 2003, 100, 11219). In the present work, this method was revisited to take into account the influence of the bilayer hydration on the emission ratiometric response of 3-HF probes. For this reason, it was necessary to deconvolute the whole fluorescence spectra into three bands corresponding to the non H-bonded forms, normal N^* and tautomer T^* forms, both participating to the ESIPT reaction, and to the H-bonded H–N^* form, excluded from this reaction. This allowed us to determine the pure N^*/T^* intensity ratio, without any contribution from the H–N^* form emission depending essentially on the bilayer hydration. This new approach allowed us to confirm the correlation we obtained between the response of 3-HF probes on dipole potential modifications and the corresponding response of the reference fluorescent probe di-8-ANEPPS, thus further confirming the potency of 3-HF probes as excellent emission ratiometric probes to measure dipole potential in lipid membranes.     

Incorporation of Siderophore Binding Sites in a Dipodal Fluorescent Sensor for Fe(III)

A new fluorescent probe 3, has been developed for the detection of Fe(III) in water based samples. The design of 3 involved the incorporation of Fe(III) binding sites observed in naturally occurring Siderophores into a synthetic sensing assembly. The probe, containing two Schiff base receptors connected to a mesitylene platform, was prepared in two steps. The dipodal sensor displayed good selectivity for Fe(III) when tested against other physiological and environmentally important metal ions, in HEPES buffered solution at pH 7.0, through a quenching of the fluorescent intensity. Stern-Volmer analysis of this quenching interaction indicated a 1:1 (host : guest) binding stoichiometry between the probe and Fe(III). The association constant, K _a calculated using the Benesi-Hildebrand equation was found to be 3.8 × 10⁴ M⁻¹. Crucially, the sensor was capable of measuring Fe(III) competitively in solutions containing both Fe(III) and Cu(II). Thus, the adoption of Fe(III) binding sites found in nature, into synthetic luminescent assemblies has proven an effective design strategy for the development of new Fe(III) probes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Large piezoelectric effects in charged, heterogeneous fluoropolymer electrets

Large piezoelectric d₃₃ coefficients around 600 pC/N are found in corona-charged non-uniform electrets consisting of elastically “soft” (microporous polytetrafluoroethylene PTFE) and “stiff” (perfluorinated cyclobutene PFCB) polymer layers. The piezoelectric activity of the two-layer fluoropolymer stack exceeds the d₃₃ coefficient of the ferroelectric ceramic lead zirconate titanate (PZT) by more than a factor of two and that of the ferroelectric polymer polyvinylidene fluoride (PVDF) by a factor of 20. Soft piezoelectric materials may become interesting for a large number of sensor and transducer applications, in areas such as security systems, medical diagnostics, and nondestructive testing. Accepted: 9 November 1999 / Published online: 3 December 1999     

Monitoring of the Proton Electrochemical Gradient in Reconstituted Vesicles: Quantitative Measurements of Both Transmembrane Potential and Intravesicular pH by Ratiometric Fluorescent Probes

Proteoliposomes carrying reconstituted yeast plasma membrane H⁺-ATPase in their lipid membrane or plasma membrane vesicles are model systems convenient for studying basic electrochemical processes involved in formation of the proton electrochemical gradient (Δμ_H ⁺) across the microbial or plant cell membrane. Δψ- and pH-sensitive fluorescent probes were used to monitor the gradients formed between inner and outer volume of the reconstituted vesicles. The Δψ-sensitive fluorescent ratiometric probe oxonol VI is suitable for quantitative measurements of inside-positive Δψ generated by the reconstituted H⁺-ATPase. Its Δψ response can be calibrated by the K⁺/valinomycin method and ratiometric mode of fluorescence measurements reduces undesirable artefacts. In situ pH-sensitive fluorescent probe pyranine was used for quantitative measurements of pH inside the proteoliposomes. Calibration of pH-sensitive fluorescence response of pyranine entrapped inside proteoliposomes was performed with several ionophores combined in order to deplete the gradients passively formed across the membrane. Presented model system offers a suitable tool for simultaneous monitoring of both components of the proton electrochemical gradient, Δψ and ΔpH. This approach should help in further understanding how their formation is interconnected on biomembranes and even how transport of other ions is combined to it.     

A Simple and Neutral Receptor Acting as a Sensitive and Switch-on Fluorescent Chemosensor for H<Subscript>2</Subscript>PO<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack>

A novel artificial anion chemosensor 1 based on 2, 2′-di (4-nitrophenylurea-β-N-yl) -1, 1′-binaphthyl is designed and synthesized for sensing anions including halide ions and oxoanions. The fluorescent emission of the binaphthyl of receptor 1, forming the hydrogen bonding with anions as the sensing mechanism, is monitored in DMSO for detecting anions. In brief, while most of the anion chemosensors are switch-off fluorescent chemosensor, or non-fluorescent sensor, receptor 1 exhibits obviously the switch-on emission during the complexation with H₂PO₄⁻.     

A Characteristic Decay Semigroup for the Resonances of Trace Class Perturbations with Analyticity Conditions of Semibounded Hamiltonians

To asymptotic complete scattering systems {M ₊+V,M ₊} on H₊:=L²(R₊,K{\mathcal{H}}_{+}:=L^{2}(\mathbf{R}_{+},{\mathcal{K}}, d λ), where M ₊ is the multiplication operator on H₊{\mathcal{H}}_{+} and V is a trace class operator with analyticity conditions, a decay semigroup is associated such that the spectrum of the generator of this semigroup coincides with the set of all resonances (poles of the analytic continuation of the scattering matrix into the lower half plane across the positive half line), i.e. the decay semigroup yields a “time-dependent” characterization of the resonances. As a counterpart a “spectral characterization” is mentioned which is due to the “eigenvalue-like” properties of resonances.     

Hydrogenated carbon clusters produced by highly charged ion impact on solid

The emission of small (hydrogenated) carbon cluster ions C_nHm ⁺ (n =2-22) upon highly charged Xe^q+ (q =20-44) impact on C₈₄ surfaces is studied by means of time-of-flight secondary ion mass spectrometry. The respective stage of hydrogenation/protonation of a certain carbon cluster ion Cn ⁺ is a strong indication for its geometrical structure. From the cluster ion yield as a function of cluster size it can be concluded, that the hydrogenation takes place after the initial carbon cluster formation. The carbon clusters seem to be emitted as an entity in agreement with “equilibrium” and “shock wave” models. Received 4 February 2000     

Synthesis, Characterization, DNA-Binding and Antiproliferative Activity of Nd(III) Complexes With N-(Nitrogen Heterocyclic) Norcantharidin Acylamide Acid

Three novel complexes [Nd(L)(NO₃)(H₂O)₂]·NO₃·2H₂O (HL¹ = N-pyrimidine norcantharidin acylamide acid, C₁₂H₁₃N₃O₄; HL² = N-pyridine norcantharidin acylamide acid, C₁₃H₁₄N₂O₄; HL³ = N-phenyl norcantharidin acylamide acid, C₁₄H₁₅NO₄) were synthesized. HL¹, HL² and HL³ are the ligand of complex(1), complex(2) and complex(3), respectively. Their structures were characterized by elemental analysis, conductivity measurement, infrared spectra and thermogravimetric analysis. The DNA-binding properties of the complexes have been investigated by fluorescence spectroscopy and viscosity measurements. The results suggest that the complexes can bind to DNA by partial intercalation. The liner Stern-Volmer quenching constant K_sq values are 3.3(±0.21)(1), 1.7(±0.19)(2) and 0.9(±0.04)(3), respectively. Complex (1) and (2) have been found to cleave pBR322 plasmid DNA at physiological pH and temperature. The test of antiproliferation activity indicates that complex(1) has strong antiproliferative ability against the SMMC7721 (IC₅₀ = 131.7 ± 23.4 μmol·L⁻¹) and A549 (IC₅₀ = 128.4 ± 19.9 μmol·L⁻¹) cell lines. The inhibition rates of complex(2) (IC₅₀ = 86.3 ± 11.3 μmol·L⁻¹) are much higher than that of NCTD (IC₅₀ = 115.5 ± 9.5 μmol·L⁻¹) and HL² (111.0 ± 5.7 μmol·L⁻¹) against SMMC7721 cell lines.     

Ratiometric and Selective Fluorescent Sensor for F<Superscript>−</Superscript> Based on Intramolecular Charge Transfer (ICT)

A simple colorimetric and ratiometric fluorescent anion sensor 1, was rationally designed and synthesized by facile one-step condensation on basis of the mechanism of intramolecular charge transfer (ICT). The sensor 1 shows more highly and selectively ability to F⁻ that induced the color changes from little yellow to purple, absorption-transferred to long wavelength and emission-transferred to short wavelength. Accordingly, ¹H NMR analysis reveals that the F⁻-induced colorimetric and fluorometric responses of 1 are simply driven by hydrogen bonding interaction between the NH protons and F⁻ ions.     

The interplay between “low” and “high” energy CP-violation in leptogenesis

We analyse, within the “flavoured” leptogenesis scenario of baryon asymmetry generation, the interplay of “low energy” CP-violation, originating from the PMNS neutrino mixing matrix U, and “high energy” CP-violation, which can be present in the matrix of neutrino Yukawa couplings, λ, and can manifest itself only in “high” energy scale processes. The type I see-saw model with three heavy right-handed Majorana neutrinos having a hierarchical spectrum is considered. The “orthogonal” parameterisation of the matrix of neutrino Yukawa couplings, which involves a complex orthogonal matrix R, is employed. In this approach the matrix R is the source of “high energy” CP-violation. Results for normal hierarchical (NH) and inverted hierarchical (IH) light neutrino mass spectrum are derived in the case of decoupling of the heaviest right-handed Majorana neutrino. It is shown that taking into account the contribution to Y _B due to the CP-violating phases in the neutrino mixing matrix U can change drastically the predictions for Y _B , obtained assuming that only “high energy” CP-violation from the R-matrix is operative in leptogenesis. In the case of the IH spectrum, in particular, there exist significant regions in the corresponding parameter space where the purely “high energy” contribution in Y _B plays a subdominant role in the production of baryon asymmetry compatible with the observations. Also at Institute of Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, 1784 Sofia, Bulgaria.     

Zero-Temperature Dynamics of ±J Spin Glasses¶and Related Models

We study zero-temperature, stochastic Ising models σ ^t on Z ^d with (disordered) nearest-neighbor couplings independently chosen from a distribution μ on R and an initial spin configuration chosen uniformly at random. Given d, call μ type ℐ (resp., type ℱ) if, for every x in Z ^d , σ _x ^t flips infinitely (resp., only finitely) many times as t→∞ (with probability one) – or else mixed type ℳ. Models of type ℒ and ℳ exhibit a zero-temperature version of “local non-equilibration”. For d=1, all types occur and the type of any μ is easy to determine. The main result of this paper is a proof that for d=2, ±J models (where μ=αδ _J +(1-α)δ_{- J} ) are type ℳ, unlike homogeneous models (type ℐ) or continuous (finite mean) μ's (type ℳ). We also prove that all other noncontinuous disordered systems are type ℳ for any d≥ 2. The ±J proof is noteworthy in that it is much less “local” than the other (simpler) proof. Homogeneous and ±J models for d≥ 3 remain an open problem. Received: 3 November 1999 / Accepted: 10 April 2000     

Thermal hopping ofμ + between “FμF” centres in NaF

Strongly hydrogen-bonded diamagnetic “FμF” centres are formed by theμ ⁺ in a wide variety of fluoride crystals. Hydrogen atoms are expected to form similar “FHF” complexes. Through the “motional narrowing” of the zero-field muon relaxation function in NaF, we have observed an Arrhenius temperature dependence of the dissociation rate of theFμF complex, yielding a binding energy of 1700 (200) K for theμ ⁺ in theFμF centre.