Eclipsed Isopropyl Conformations of Two Dimeric Hydrazines

The X-ray structures of 4,10-di-tert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2(3,6)]tetradecane (s4iPr) and its 4,9-di-tert-butyl-5,10-diisopropyl isomer (a4iPr) are reported. Both compounds are in conformations having their in-N-alkyl groups (directed toward the central CH-CH bond of the molecule) anti to each other, as expected from previous work. The principal feature of interest is that one in-isopropyl group in each compound is in an eclipsed conformation, NN,C(alpha)Me twist angle -0.5(5) degrees for s4iPr and -6.4(4) degrees for a4iPr. Low energy (somewhat less) eclipsed in-isopropyl conformations are predicted by both molecular mechanics (MM2) and semiempirical quantum mechanical (AM1) calculations. The asymmetry of the potentially C(2) symmetric a4iPr because the two in-isopropyl groups are in different rotamers is apparently not a result of crystal packing forces, because a conformation with different isopropyl rotamers is the more stable one by at least 1.0 kcal/mol in solution, determined by (13)C-NMR spectroscopy. This result is not predicted by either calculation method. The "monomer", 2-tert-butyl-3-isopropyl-2,3-diazabicyclo[2.2.2]octane (3), proves to be a poor model for the conformations of 4iPr.     

Approximate minimum-cost multicommodity flows in\tilde O(ɛ −2 KNM) timetime

We show that an ε-approximate solution of the cost-constrainedK-commodity flow problem on anN-nodeM-arc network,G can be computed by sequentially solving O(K(? ^?2+logGK) logGM log (G? ^?1 GK)) single-commodity minimum-cost flow problems on the same network. In particular, an approximate minimum-cost multicommodity flow can be computed in $\tilde O$ (G? ^?2 GKNM) running time, where the notation Õ(·) means “up to logarithmic factors”. This result improves the time bound mentioned by Grigoriadis and Khachiyan [4] by a factor ofM/N and that developed more recently by Karger and Plotkin [8] by a factor of? ^?1. We also provide a simple $\tilde O$ (NM)-time algorithm for single-commodity budget-constrained minimum-cost flows which is $\tilde O$ (? ^?3) times faster than the algorithm developed in the latter paper.     

Distance distributions and dynamics of a zinc finger peptide from fluorescence resonance energy transfer measurements

Time-resolved fluorescence resonance energy transfer (FRET) measurements were used to measure distance distributions and intramolecular dynamics (site-to-site diffusion) of a 28-residue single-domain zinc finger peptide in the absence and presence of zinc ion. Energy transfer was measured between TRP₁₄ and a N-terminal DNS group. As expected, the TRP-to-DNS distance distribution for zinc-bound peptide is shorter and narrower (R _av=11.2 Å,hw=2.8 Å) than the metal-free peptide (R _av=20.1 Å,hw=14.5 Å). The degree of mutual donor-to-acceptor diffusion (D) was also determined for these distributions. For zinc-bound peptide there is no detectible diffusion (D0.2 Ų/ns), whereas for metal-free peptide a considerable amount of motion is occurring between the donor and the acceptor (D=12 Ų/ns). These results indicate that the zinc-bound peptide folds into a unique, well-defined conformation, whereas the metal-free conformation is flexible and rapidly changing. The absence of detectible mutual site-to-site diffusion between the donor and the acceptor in the metal-bound zinc finger peptide indicates that intramolecular motion is essentially frozen out, on the FRET time scale, as a consequence of zinc coordination.Dedicated to the memory of Barbara D. Wells.     

Distance-dependent fluorescence quenching ofN-acetyl-l-tryptophanamide by acrylamide

We examined the time-dependent intensity decays ofN-acetyl-l-tryptophanamide (NATA) when collisionally quenched by acrylamide in propylene glycol over a range of temperatures. The intensity decays of NATA became increasingly heterogeneous in the presence of acrylamide. The NATA intensity decays were not consistent with the Collins-Kimball radiation boundary condition (RBC) model for quenching. The steady-state Stern-Volmer plots show significant upward curvature, and quenching of NATA by acrylamide was observed even in vitrified propylene glycol, where translational diffusion cannot occur during the lifetime of the excited state. These frequencydomain and steady-state data indicate a through-space quenching interaction between NATA and acrylamide, and the results are consistent with a rate constant for quenching that depends exponentially on the fluorophore-quencher separation distance. The exponential distance-dependent rate of quenching also explains the upward curvature of the Stern-Volmer plot, and the steady-state data aid in determining the interaction distance between NATA and acrylamide. These results suggest that the distance-dependent quenching rates need to be considered in the interpretation of acrylamide quenching of proteins.     

W-Algebras,new rational models and completeness of thec=1 classification

Two series ofW with two generators are constructed from chiral vertex operators of a free field representation. Ifc=1–24k, there exists aW(2, 3k) algebra for k ₊/2 and aW(2, 8k) algebra for k ₊/4. All possible lowest-weight representations, their characters and fusion rules are calculated proving that these theories are rational. It is shown, that these non-unitary theories complete the classification of all rational theories with effective central chargec _eff=1. The results are generalized to the case of extended supersymmetric conformal algebras.     

Lattice and continuum wavelets and the block renormalization group

We obtain a resolution of the identity operator, for functions on a latticeZ ^d, which is derived from the block renormalization group. We use eigenfunctions of the terms of the decomposition to form a basis forl ₂(Z^d) and show how the basis is generated from lattice wavelets. The lattice spacing is taken to zero and continuum wavelets are obtained.     

The effects of temperature and pressure on the lifetime of benzophenone emission

The variation in the lifetime of flash-excited gaseous benzophenone with pressure and temperature indicates that (1) self-quenching is a relatively inefficient process for the long-lived emission, k_sq = 9 × 10⁵ M^?1 s^?1 (estimated from solution data) at 25°C and 1.2 × 10⁷ M^?1 s^?1 at 170°C and (2) the lifetime decreases with increasing temperature as a result of photochemical and photophysical decay pathways which have significant activation energies. The importance of diffusion to the walls on lifetime measurements is discussed.     

Synthesis, structure, theoretical studies, and Ligand exchange reactions of monomeric, T-shaped arylpalladium(II) halide complexes with an additional, weak agostic interaction

A series of monomeric arylpalladium(II) complexes LPd(Ph)X (L = 1-AdPtBu2, PtBu3, or Ph5FcPtBu2 (Q-phos); X = Br, I, OTf) containing a single phosphine ligand have been prepared. Oxidative addition of aryl bromide or aryl iodide to bis-ligated palladium(0) complexes of bulky, trialkylphosphines or to Pd(dba)2 (dba = dibenzylidene acetone) in the presence of 1 equiv of phosphine produced the corresponding arylpalladium(II) complexes in good yields. In contrast, oxidative addition of phenyl chloride to the bis-ligated palladium(0) complexes did not produce arylpalladium(II) complexes. The oxidative addition of phenyl triflate to PdL2 (L = 1-AdPtBu2, PtBu3, or Q-phos) also did not form arylpalladium(II) complexes. The reaction of silver triflate with (1-AdPtBu2)Pd(Ph)Br furnished the corresponding arylpalladium(II) triflate in good yield. The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear to be stabilized by a weak agostic interaction of the metal with a ligand C-H bond positioned at the fourth-coordination site of the palladium center. The strength of the Pd.H bond, as assessed by tools of density functional theory, depended upon the donating properties of the ancillary ligands on palladium.     

Selective mixed coupling of carboxylic acids (II). — photolysis of unsymmetrical diacylperoxides with alkenyl-, halo-, keto-, carboxyl-groups and a chiral α-carbon. Comparison with the mixed kolbe electrolysis

Alkenoyl and functionalized alkanoyl dodecanoyl peroxides are prepared in 70 to 97 % yield and photolyzed at ?78° C. Thereby 4- to 10-alkenoyl and 4-alkanoyl peroxides afford good yields (56 – 68 %) of unsymmetrical coupling products. Similarly α- to σ-haloalkanoyl, cholanoyl or 3- and 4-carboxyalkanoyl peroxides can be coupled (40 – 70 %). The α-chiral diacyl peroxide ls undergoes the photochemical coupling reaction with 80 % retention of its configuration. The photolysis of diacyl peroxides at ?78° C proves to be a favorable supplement of the Kolbe-electrolysis in cases, where the electrolysis fails or produces low yields.     

7-Deazaadenosine: Oligoribonucleotide building block synthesis and autocatalytic hydrolysis of base-modified hammerhead ribozymes

A 7-deazaadenosine ( = tubercidin; c⁷A; 1 ) building block for solid-phase oligoribonucleotide synthesis was prepared. The amino group of 1 was protected with the (dimethylamino)methylidene residue (→ 3 ), and the monomethoxytrityl group was introduced at OH? C(5′) (→ 4 ). Protection of OH? C(2′) was carried out by silylation, showing that use of the (i-Pr)₃Si group resulted in high 2′-O-selectivity (→ 5b , 80%). Reaction of 5b with PCl₃ afforded the phosphonate 7 which was used in solid-phase oligoribonucleotide synthesis. The autocatalytic hydrolysis of hammerhead ribozymes using pG-G-G-A-G-U-C-A-G-U-C-C-C-U-U-C-G-G-G-G-A-C-U-C-U-G-A-A-G-A-G-G-C-G-C as substrate strand (S) and modified G-C-G-C-C-G-A-A-A-C-U-C-C-C as enzyme strand (E) was studied. When c⁷A replaced A¹³ or A¹⁴, a small decrease of catalytic activity was observed, while modification in position A¹⁵ enhanced the autocatalytic hydrolysis. The results demonstrate, that the atom N(7) of adenosine in any of these positions is not crucial for ribozyme action.