Equilibrium Formation of Stable All‐Silicon Versions of 1,3‐Cyclobutanediyl

Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si₃Tip₄ (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR₂CH₂)(NtBu)₂]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)₂(NtBu)₂Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate.     

Bestimmung der Langkettenverzweigung von Hochdruckpolylithylen durch Streulicht- und Viskosit?tsmessungen

Ohne Zusammenfassung     

Rigorous Analysis of Discontinuous Phase Transitions via Mean-Field Bounds

 We consider a variety of nearest-neighbor spin models defined on the d-dimensional hypercubic lattice ℤ ^d . Our essential assumption is that these models satisfy the condition of reflection positivity. We prove that whenever the associated mean-field theory predicts a discontinuous transition, the actual model also undergoes a discontinuous transition (which occurs near the mean-field transition temperature), provided the dimension is sufficiently large or the first-order transition in the mean- field model is sufficiently strong. As an application of our general theory, we show that for d sufficiently large, the 3-state Potts ferromagnet on ℤ ^d undergoes a first-order phase transition as the temperature varies. Similar results are established for all q-state Potts models with q≥3, the r-component cubic models with r≥4 and the O(N)-nematic liquid-crystal models with N≥3. Received: 22 July 2002 / Accepted: 12 January 2003 Published online: 5 May 2003 RID="⋆" ID="⋆" ? Copyright rests with the authors. Reproduction of the entire article for non-commercial purposes is permitted without charge. Communicated by J. Z.Imbrie     

General theory of lee-yang zeros in models with first-order phase transitions

We present a general, rigorous theory of Lee-Yang zeros for models with first-order phase transitions that admit convergent contour expansions. We derive formulas for the positions and the density of the zeros. In particular, we show that, for models without symmetry, the curves on which the zeros lie are generically not circles, and can have topologically nontrivial features, such as bifurcation. Our results are illustrated in three models in a complex field: the low-temperature Ising and Blume-Capel models, and the q-state Potts model for large q.     

Dynamic and redundant regulation of LRRK2 and LRRK1 expression

Background  

Mutations within the leucine-rich repeat kinase 2 (LRRK2) gene account for a significant proportion of autosomal-dominant and some late-onset sporadic Parkinson's disease. Elucidation of LRRK2 protein function in health and disease provides an opportunity for deciphering molecular pathways important in neurodegeneration. In mammals, LRRK1 and LRRK2 protein comprise a unique family encoding a GTPase domain that controls intrinsic kinase activity. The expression profiles of the murine LRRK proteins have not been fully described and insufficiently characterized antibodies have produced conflicting results in the literature.     

Single-machine scheduling against due dates with past-sequence-dependent setup times

Recently Koulamas and Kyparisis [Koulamas, C., Kyparisis, G.J., in press. Single-machine scheduling with past-sequence-dependent setup times. European Journal of Operational Research] introduced past-sequence-dependent setup times to scheduling problems. This means that the setup time of a job is proportionate to the sum of processing times of the jobs already scheduled. Koulamas and Kyparisis [Koulamas, C., Kyparisis, G.J., in press. Single-machine scheduling with past-sequence-dependent setup times. European Journal of Operational Research] were able to show for a number of single-machine scheduling problems with completion time goals that they remain polynomially solvable. In this paper we extend the analysis to problems with due dates. We demonstrated that some problems remain polynomially solvable. However, for some other problems well-known polynomially solution approaches do not guarantee optimality any longer. Consequently we concentrated on finding polynomially solvable special cases.     

Synthesis-guided structure revision of the sarcodonin, sarcoviolin, and hydnellin natural product family

A sweeping structural revision of the sarcodonin natural product family (published structures 1a-13a) is proposed after extensive studies aimed at their chemical synthesis. Key features of revised structure 1b include replacement of the N,N-dioxide moiety with an oxime, ring-opening of the central diketopiperazine, and transposition of the terphenyl wing from the 1β-2β position of 1a to the 2β-3β position of 1b. This structure revision arose from the serendipitous synthesis of a benzodioxane aminal (44) whose structure was unambiguously determined by X-ray crystallography and whose spectral properties bore considerable resemblance to the published data for the sarcodonins. A versatile new method for O-arylation of hydroxamic acids is also reported herein, as well as a manganese(III)-mediated α-oxidation of hydroxamic acids to aminals.     

Unexpected electron transfer in cryptochrome identified by time-resolved EPR spectroscopy

Subtle differences in the local sequence and conformation of amino acids can result in diversity and specificity in electron transfer (ET) in proteins, despite structural conservation of the redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of the ET partners, and thus the stabilization of the charge-separated states, contribute substantially.