Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Investigation of dielectric, piezoelectric and ferroelectric properties of b-axis grown triglycine sulphate single crystal

Large single crystal of triglycine sulphate (dimension 100 mm along monoclinic b-axis and 15 mm in diameter) was grown using the unidirectional solution growth technique. The X-ray diffraction studies confirmed the growth/long axis to be b-axis (polar axis). The dielectric studies were carried out at various temperatures to establish the phase transition temperature. The frequency response of the dielectric constant, dielectric loss and impedance of the crystal along the growth axis, was monitored. These are typically characterized by strong resonance peaks in the kHz region. The piezoelectric coefficients like stiffness constant (C), elastic coefficient (S), electromechanical coupling coefficient (k) and d (31) were calculated using the resonance-antiresonance method. Polarization (P)-Electric field (E) hysteresis loops were recorded at various temperatures to find the temperature-dependent spontaneous polarization of the grown crystal. The pyroelectric coefficients were determined from the pyroelectric current measurement by the Byer and Roundy method. The ferroelectric domain patterns were recorded on (010) plane using scanning electron microscopy and optical microscopy.

Anomalous X-ray scattering study of local structures in the superionic conducting glass (AgBr)0.4 (Ag2O)0.3 (GeO2)0.3

The local structural information in the near-neighbor region of superionic conducting glass (AgBr)0.4(Ag2O)0.3(GeO2)0.3 has been estimated from the anomalous X-ray scattering (AXS) measurements using Ge and Br K absorption edges. The possible atomic arrangements in the near-neighbor region of this glass were obtained by coupling the results with the least-squares variational method so as to reproduce two differential intensity profiles for Ge and Br as well as the ordinary scattering profile. The coordination number of oxygen around Ge is found to be 3.6 at a distance of 0.176 nm, suggesting the GeO4 tetrahedral unit as the probable structural entity in this glass. Moreover, the coordination number of Ag around Br is estimated as 6.3 at a distance of 0.284 nm, suggesting an arrangement similar to that in crystalline AgBr.

Suppressed rf dissipation in 107Ag17+ ion irradiated Bi2Sr2CaCu2O8 single crystals by enhanced flux line tilt modulus

We have studied the isothermal, magnetic field (H‖c) dependent rf power P(H) dissipation (Hrf‖a) in the superconducting state of Bi2Sr2CaCu2O8 single crystals prior to and after irradiation with 250 MeV 107Ag17+ ions. In the pristine state, P(H) shows an initial decrease with increase in field, reaches a minimum at HM(T) and increases monotonically for H>HM(T). This behavior arises when the electromagnetic coupling between the pancake vortices in adjacent CuO layers becomes dominant on increasing the field and minimizes the distortions of the flux lines by confining the 2D vortices. In the post irradiated state, such an initial decrease and the minimum in P(H) is not observed but only a much reduced rf dissipation that monotonically increases with field from H = 0 onwards is seen. We attribute this difference to the strong enhancement of the tilt modulus C44 of the flux lines on irradiation when the pancake vortices in adjacent CuO bilayers are pinned along the track forming a well-stacked flux line in the field direction (‖c). We have also observed that the rf dissipation disappears at a certain temperature Tsf, at which the normal core of the flux line becomes commensurate with the columnar track diameter.

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.

Oxygen displacement in a 107Ag17+ ion irradiated Bi2Sr2CaCu2O8 single crystal

We have studied the magnetic field (H∥c) dependent rf dissipation (Hrf∥a) in an as-grown Bi2Sr2CaCu2O8 single crystal prior to and after irradiation with 250 MeV 107Ag17+ ions. In a comparison of the responses from the as-grown crystal with an air-annealed crystal, features due to oxygen deficient regions acting as weak links in the former are identified. These features disappear immediately after irradiation of the as-grown crystal. We attribute such behavior to the displacement of oxygen from columnar tracks to deficient regions thus eliminating the weak links. Losses from the same irradiated as-grown crystal stored at 300 K for 60 days show that the features similar but not identical to those observed in the pristine state have reappeared implying that the displaced oxygen is in a metastable configuration in the deficient regions and hence is mobile due to thermal effects even at 300 K.

Structural, optical, and electrical properties of bulk single crystals of InAsxSb(1-x) grown by rotatory Bridgman method

Radially-homogeneous and single-phase InAsxSb(1−x) crystals, up to 5.0 at. % As concentration, have been grown using the rotatory Bridgman method. Single crystallinity has been confirmed by x-ray and electron diffraction studies. Infrared transmission spectra show a continuous decrease in optical energy gap with the increase of arsenic content in InSb. The measured values of mobility and carrier density at room temperature (for x = .05) are 5.6×104 cm2/V s and 2.04×1016 cm−3, respectively.

Scattering theory and linear optimal control: Regulator and servo problems

In this paper, several known computational solutions are readily obtained in a very natural way for the linear regulator, fixed end-point and servo-mechanism problems using a certain frame-work from scattering theory. The relationships between the solutions to the linear regulator problem with different terminal costs and the interplay between the forward and backward equations have enabled a concise derivation of the partitioned equations, the forward-backward equations, and Chandrasekhar equations for the problem. These methods have been extended to the fixed end-point, servo, and tracking problems.

Transport and magnetic properties of Nd1-xPbxMnO3 single crystals

Transport and magnetic properties of flux-grown Nd1−xPbxMnO3 single crystals (x=0.15–0.5) are studied in the temperature range 300–77 K and 280–2 K, respectively. Magnetization measurements with a superconducting quantum interference device confirm a paramagnetic to ferromagnetic transition around 110, 121, 150, 160, and 178 K for x=0.15, 0.2, 0.3, 0.4, and 0.5, respectively. Four probe resistivity measurements at low temperatures show a monotonic increase for x=0.15 which represents a ferromagnetic insulating (FMI) phase. For Nd0.8Pb0.2MnO3 there is a slope change present in the resistivity profile at 127 K where metal to insulator transition (MI) sets in. For x=0.3 this MI transition is more prominent. However, both these samples have FMI phase at low temperature. When the concentration of lead increases (x>0.3) the sample displays a clear insulator to metal transition with a low temperature ferromagnetic metallic phase. On the basis of these measurements we have predicted the phase diagram of Nd1−xPbxMnO3. Magnetization measurements by a vibration sample magnetometer point out the appreciable differences between zero field cooled and field cooled profiles below the ferromagnetic to paramagnetic transition temperature for all x. These are indicative of magnetic frustration.

Effect of surface on the conductance characteristics of Au‐Bi2Sr2CaCu2O8+δ (single crystal) point contact junctions

We report the effect of surface treatments on the dynamic conductance curves (G=dI/dV‐V) of Au‐Bi2Sr2CaCu2O8+δ (single crystal) point contact junctions of variable junction conductances (100 mS≳G≳100 μS). We find that if the crystal surface is cleaved freshly just prior to making contacts, all irreproducible sharp multiple features often observed in tunneling data of Bi(2212) oxide superconductors disappear. If the cleaved crystal surfaces are left under ambient conditions for a few days and the tunneling experiments are repeated, these multiple features reappear. We also find that if the current in the junction is made to pass predominantly through the bulk (and not along the surface), gap features are sharper. The observed conductance curves are fitted to a modified model [G. E. Blonder et al., Phys. Rev. B 25, 4515 (1982)] and estimated gap values are Δ≂28 to 30 meV corresponding to the ratio 2Δ/kBTc ≂ 7.5 with lifetime broadening Γ/Δ≂0.2. We conclude that the sharp multiple features observed in Bi(2212) tunneling curves has no intrinsic origin in the bulk and they arise from the surface only.

Maximum Rate of Unitary-Weight, Single-Symbol Decodable STBCs

It is well known that the space-time block codes (STBCs) from complex orthogonal designs (CODs) are single-symbol decodable/symbol-by-symbol decodable (SSD). The weight matrices of the square CODs are all unitary and obtainable from the unitary matrix representations of Clifford Algebras when the number of transmit antennas n is a power of 2. The rate of the square CODs for n = 2(a) has been shown to be a+1/2(a) complex symbols per channel use. However, SSD codes having unitary-weight matrices need not be CODs, an example being the minimum-decoding-complexity STBCs from quasi-orthogonal designs. In this paper, an achievable upper bound on the rate of any unitary-weight SSD code is derived to be a/2(a)-1 complex symbols per channel use for 2(a) antennas, and this upper bound is larger than that of the CODs. By way of code construction, the interrelationship between the weight matrices of unitary-weight SSD codes is studied. Also, the coding gain of all unitary-weight SSD codes is proved to be the same for QAM constellations and conditions that are necessary for unitary-weight SSD codes to achieve full transmit diversity and optimum coding gain are presented.

Usefulness of in Situ Single Crystal to Single Crystal Transformation (SCSC) Studies in Understanding the Temperature-Dependent Dimensionality Cross-over and Structural Reorganization in Copper-Containing Metal-Organic Frameworks (MOFs)

Two copper-containing compounds [Cu(3)(mu(3)-OH)(2)-(H(2)O)(2){(SO(3))-C(6)H(3)-(COO)(2)}(CH(3)COO)] , I, and [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, II, were prepared using sulphoisophthalic and nitroisophthalic acids. The removal of the coordinated water molecules in the compounds was investigated using in situ single crystal to single crystal (SCSC) transformation studies, temperature-dependent powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). The efficacy of SCSC transformation studies were established by the observation of dimensionality cross-over from a two-dimensional (I) to a three-dimensional structure, Cu(6)(mu(3)-OH)(4){(SO(3))-C(6)H(3)-(COO)(2)}(2)(CH(3)COO)(2), Ia, during the removal of the coordinated water molecules. Compound H exhibited a structural reorganization forming Cu(5)(mu(2)-OH)(2){(NO(2))C(6)H(3)-(COO)(2))(4)], Ha, possessing trimeric (Cu(3)O(12)) and dimeric (Cu(2)O(8)) copper clusters. The PXRD studies indicate that the three-dimensional structure (Ia) is transient and unstable, reverting back to the more stable two-dimensional structure (I) on cooling to room temperature. Compound Ha appears to be more stable at room temperature. The rehydration/dehydration studies using a modified TGA setup suggest complete rehydration of the water molecules, indicating that the water molecules in both compounds are labile. A possible model for the observed changes in the structures has been proposed. Magnetic studies indicate changes in the exchanges between the copper centers in Ha, whereas no such behavior was observed in Ia.