Comprehensive study of blue and green multi-quantum-well light-emitting diodes grown on conventional and lateral epitaxial overgrowth GaN

Growths of blue and green multi-quantum wells (MQWs) and light-emitting diodes (LEDs) are realized on lateral epitaxial overgrowth (LEO) GaN, and compared with identical structures grown on conventional GaN. Atomic force microscopy is used to confirm the significant reduction of dislocations in the wing region of our LEO samples before active-region growth. Differences between surface morphologies of blue and green MQWs are analyzed. These MQWs are integrated into LEDs. All devices show a blue shift in the electroluminescence (EL) peak and narrowing in EL spectra with increasing injection current, both characteristics attributed to the band-gap renormalization. Green LEDs show a larger EL peak shift and a broader EL spectrum due to larger piezoelectric field and more indium segregation in the MQWs, respectively. Blue LEDs on LEO GaN show a higher performance than those on conventional GaN; however, no performance difference is observed for green LEDs on LEO GaN versus conventional GaN. The performance of the green LEDs is shown to be primarily limited by the active layer growth quality.     

Squaramido-based receptors: applicability of molecular interaction potential to molecular recognition of polyalkylammonium compounds

 A computational study of the mechanism of host–guest complexation between quaternary ammonium compounds and squaramido-based tripodal receptors has been carried out. Semiempirical molecular orbital calculations, which are in qualitative agreement with experimental results have been performed using the PM3 Hamiltonian. Molecular interaction potential (MIP) maps were used to analyze the suitability of both host and guest binding units for a high-affinity recognition process. MIP calculations were computed from PM3 wavefunctions of the corresponding ammonium cations and dimethyl squaramide as a model compound for the hydrogen-bond-acceptor unit of the receptors. MIP analyses are helpful for understanding the host–guest process from the point of view of the double-complementarity principle. Received: 23 June 1999 / Accepted: 22 September 1999 / Published online: 17 January 2000     

On the conformational preferences of nylons-n: Analysis of the intramolecular interactions in even nylons-n

The relative stability between the fully-extended and quasi-extended conformations characteristic of the α and β forms of nylons, respectively, has been investigated for both even and odd nylons-n using ab initio quantum mechanical calculations. For nylon-2 the fully-extended is the most favored conformation and its stability clearly increases with the number of residues. On the other hand, for nylons-4 and -6 the quasi-extended conformation is slightly favored with respect to the fully-extended one, although the relative energy between the two conformations decreases with the number of residues. Thus, the fully-extended conformation is predicted as the most stable conformation in compounds with a larger number of residues for nylons-4 and -6. On the other hand, the quasi-extended conformation is the most favored for odd nylons-n and even nylons-n with n > 6. The results have been explained in terms of the intramolecular electrostatic interactions that appear in nylons-2, -4 and -6 between the N H and CO groups of a residue.     

Forward particle production in π− p andK − p collisions at 58 GeV/c and comparison with quark models

We present single inclusive π^±, π⁰ andK ^± spectra in the forward fragmentation region (x>0.2,p _T <1.5 GeV/c) as well as correlations between two charged particles. The data were recorded in an unseparated negative hadron beam at the CERN SPS using a large acceptance forward spectrometer. Our maasurements are compared in detail with several models which emphasise the role of the beam valence quarks in this production process. The connection to measurements at largep _T is also investigated.     

Bound coefactor/dual enzyme electrode system for l-alanine

A dual enzyme-bound coenzyme electrode system for quantifying l-alanine is described. Commercially available dextran-bound NAD was incorporated into an l-alanine dehydrogenase (E.C. 1.4.1.1)/l-lactate dehydrogenase (E.C. 1.1.1.27) enzyme system and held at the surface of a potentiometric ammonia gas sensor. Using this system, l-alanine calibration curves with a slope of 45 mV/decade and 10^?5 M detection limit were obtained with a sensor lifetime of at least 10 days. This system is potentially useful for the clinical determination of l-alanine in serum.     

Synthesis of novel simplified sarcodictyin/eleutherobin analogs with potent microtubule-stabilizing activity, using ring closing metathesis as the key-step

The synthesis of a number of novel simplified eleutheside analogs with potent tubulin-assembling and microtubule-stabilizing properties is described, using ring closing metathesis as the key-step for obtaining the 6-10 fused bicyclic ring system. The RCM precursors were synthesized starting from aldehyde 3 [prepared in 6 steps on a multigram scale from R-(−)-carvone in 30% overall yield] via multiple stereoselective Brown allylations. Second generation RCM catalyst 13 gave the desired ring closed 10-membered carbocycles as single Z stereoisomers in good yields. The RCM stereochemical course (100% Z) likely reflects thermodynamic control. The crucial role of the protecting groups of the homoallylic and allylic substituents for the efficiency of the RCM reactions is discussed. These simplified analogs of the natural product (lacking inter alia the C-4/C-7 ether bridge) retain potent microtubule-stabilizing activity. However, the cytotoxicity tests did not parallel the potent tubulin-assembling and microtubule-stabilizing properties: limited cytotoxicity was observed against three common tumor cell lines (human ovarian carcinoma and human colon carcinoma cell lines, IC₅₀ in the μM range given in Table 2), three orders of magnitude less than paclitaxel (IC₅₀ in the nM range).     

Bridging nitrate groups in [Mn(4)O(3)(NO(3))(O(2)CMe)(3)(R(2)dbm)(3)] (R = H, Et) and [Mn(4)O(2)(NO(3))(O(2)CEt)(6)(bpy)(2)](ClO(4)): acidolysis routes to tetranuclear manganese carboxylate complexes

New synthesis procedures are described to tetranuclear manganese carboxylate complexes containing the [Mn(4)O(2)](8+) or [Mn(4)O(3)X](6+) (X(-) = MeCO(2)(-), F(-), Cl(-), Br(-), NO(3)(-)) core. These involve acidolysis reactions of [Mn(4)O(3)(O(2)CMe)(4)(dbm)(3)] (1; dbm is the anion of dibenzoylmethane) or [Mn(4)O(2)(O(2)CEt)(6)(dbm)(2)] (8) with HX (X(-) = F(-), Cl(-), Br(-), NO(3)(-)); high-yield routes to 1 and 8 are also described. The X(-) = NO(3)(-) complexes [Mn(4)O(3)(NO(3))(O(2)CR)(3)(R'(2)dbm)(3)] (R = Me, R' = H (6); R = Me, R' = Et (7); R = Et, R' = H (12)) represent the first synthesis of the [Mn(4)O(3)(NO(3))](6+) core, which contains an unusual eta(1):mu(3)-NO(3)(-) group. Treatment of known [Mn(4)O(2)(O(2)CEt)(7)(bpy)(2)](ClO(4)) with HNO(3) gives [Mn(4)O(2)(NO(3))(O(2)CEt)(6)(bpy)(2)](ClO(4)) (15) containing a eta(1):eta(1):mu-NO(3)(-) group bridging the two body Mn(III) ions of the [Mn(4)O(2)](8+) butterfly core. Complex 7 x 4CH(2)Cl(2) crystallizes in space group P2(1)2(1)2(1) with (at -168 degrees C) a = 21.110(3) A, b = 22.183(3) A, c = 15.958(2) A, Z = 4, and V = 7472.4(3) A(3). Complex 15 x (3)/(2)CH(2)Cl(2) crystallizes in space group P2(1)/c with (at -165 degrees C) a = 26.025(4) A, b = 13.488(2) A, c = 32.102(6) A, beta = 97.27(1) degrees, Z = 8, and V = 11178(5) A(3). Complex 7 contains a [Mn(4)(mu(3)-O)(3)(mu(3)-NO(3))](6+) core (3Mn(III), Mn(IV)) as seen for previous [Mn(4)O(3)X](6+) complexes. Complex 15 contains a butterfly [Mn(4)(mu(3)-O)(2)](8+) core. (1)H NMR spectra have been recorded for all complexes reported in this work and the various resonances assigned. All complexes retain their structural integrity on dissolution in chloroform and dichloromethane. Magnetic susceptibility (chi(M)) data were collected on 12 in the 5-300 K range in a 10.0 kG (1 T) field. Fitting of the data to the theoretical chi(M) vs T expression appropriate for a [Mn(4)O(3)X](6+) complex of C(3)(v)() symmetry gave J(34) = -23.9 cm(-)(1), J(33) = 4.9 cm(-)(1), and g = 1.98, where J(34) and J(33) refer to the Mn(III)Mn(IV) and Mn(III)Mn(III) pairwise exchange interactions, respectively. The ground state of the molecule is S = 9/2, as found previously for other [Mn(4)O(3)X](6+) complexes. This was confirmed by magnetization data collected at various fields and temperatures. Fitting of the data gave S = 9/2, D = -0.45 cm(-1), and g = 1.96, where D is the axial zero-field splitting parameter.     

Three-Photon Infrared Stimulation of Endogenous Neuroreceptors in Vivo

To interrogate neural circuits and crack their codes, in vivo brain activity imaging must be combined with spatiotemporally precise stimulation in three dimensions using genetic or pharmacological specificity. This challenge requires deep penetration and focusing as provided by infrared light and multiphoton excitation, and has promoted two-photon photopharmacology and optogenetics. However, three-photon brain stimulation in vivo remains to be demonstrated. We report the regulation of neuronal activity in zebrafish larvae by three-photon excitation of a photoswitchable muscarinic agonist at 50 pM, a billion-fold lower concentration than used for uncaging, and with mid-infrared light of 1560 nm, the longest reported photoswitch wavelength. Robust, physiologically relevant photoresponses allow modulating brain activity in wild-type animals with spatiotemporal and pharmacological precision. Computational calculations predict that azobenzene-based ligands have high three-photon absorption cross-section and can be used directly with pulsed infrared light. The expansion of three-photon pharmacology will deeply impact basic neurobiology and neuromodulation phototherapies.     

Diastereoselective synthesis of allosecurinine and viroallosecurinine from menisdaurilide

A new and versatile synthetic route to Securinega alkaloids is reported. The first synthesis of allosecurinine has been accomplished in seven steps and 40% yield, starting from (+)-menisdaurilide, using a vinylogous Mannich reaction as the key transformation. Similarly, viroallosecurinine has been synthesized from (-)-menisdaurilide.