Overcomplete mechanisms of plastic collapse

The analysis of regular mechanisms of plastic collapse for plane frames may be done by simple statics. By contrast, the solutions of analogous problems for space frames require the use of deformation equations; the mere formation of a collapse mechanism does not make the collapsing portion of a frame soluble by statics alone. Further, the number of plastic hinges for regular collapse of a plane frame is determinable, but no rule can be constructed for the number of hinges in a space frame; indeed, space frames can collapse by mechanisms which appear to have more degrees of freedom than are necessary, and are in this sense over-complete.     

Inelastic interactions with deuterons at very high energies

Cross sections for inelastic reactions of hadrons, photons and leptons with deuterons are derived from the Coherent Tube Model for particle-nucleus collisions. Predictions are compared with recent experimental data. Good agreement between experiments and theory is demonstrated.     

Optimal mass production

It is often desirable to perform a “sensitivity analysis” by perturbing the data given with a problem. Motivated by serial and nonserial dynamic programming, we define a variety of sensitivity analysis problems, produce algorithms, and obtain lower bound results.     

Cut-Free Ordinary Sequent Calculi for Logics Having Generalized Finite-Valued Semantics

The paper presents a method for transforming a given sound and complete n-sequent proof system into an equivalent sound and complete system of ordinary sequents. The method is applicable to a large, central class of (generalized) finite-valued logics with the language satisfying a certain minimal expressiveness condition. The expressiveness condition decrees that the truth-value of any formula φ must be identifiable by determining whether certain formulas uniformly constructed from φ have designated values or not. The transformation preserves the general structure of proofs in the original calculus in a way ensuring preservation of the weak cut elimination theorem under the transformation. The described transformation metod is illustrated on several concrete examples of many-valued logics, including a new application to information sources logics.     

Controlled synthesis of cell-laden microgels by radical-free gelation in droplet microfluidics

Micrometer-sized hydrogel particles that contain living cells can be fabricated with exquisite control through the use of droplet-based microfluidics and bioinert polymers such as polyethyleneglycol (PEG) and hyperbranched polyglycerol (hPG). However, in existing techniques, the microgel gelation is often achieved through harmful reactions with free radicals. This is detrimental for the viability of the encapsulated cells. To overcome this limitation, we present a technique that combines droplet microfluidic templating with bio-orthogonal thiol-ene click reactions to fabricate monodisperse, cell-laden microgel particles. The gelation of these microgels is achieved via the nucleophilic Michael addition of dithiolated PEG macro-cross-linkers to acrylated hPG building blocks and does not require any initiator. We systematically vary the microgel properties through the use of PEG linkers with different molecular weights along with different concentrations of macromonomers to investigate the influence of these parameters on the viability and proliferation of encapsulated yeast cells. We also demonstrate the encapsulation of mammalian cells including fibroblasts and lymphoblasts.     

Ladder oligo(m-aniline)s: derivatives of azaacenes with cross-conjugated π-systems

We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-membered rings employed Pd-catalyzed aminations and Friedel-Crafts-based ring closures. Structures were confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra. All compounds have planar "azaacene" moieties. The experimental band gaps E(g) ≈ 3.5-3.65 eV, determined by the UV-vis absorption onsets, were in agreement with the TD-DFT-computed vertical excitation energies to the S(1) state. Fluorescence quantum yields of up to 20% were found. Electrochemically estimated HOMO energies of -4.8 eV suggested propensity for a facile one-electron oxidation and just sufficient environmental stability toward oxygen (O(2)). For two oligomers with "tetraazanonacene" moieties, potentials of E(4+/3+) ≈ 1.6-1.7 V vs SCE were determined for four-electron oxidation to the corresponding tetraradical tetracations.     

Conformational properties of α- and β-azabicyclane opiates. The effect of conformation on pharmacological activity

Conformational energy calculations using the MM 2 (molecular mechanics II) program are reported for diastereoisomeric α- and β-azabicyclanes (3-methyl-9-methoxy-9-phenyl-3-azabicyclo [3.3.1] nonanes) which are prototypical phenyl-axial and phenyl-equatorial opiates. After energy minimization, both compounds are found to prefer a chair–chair conformation of the piperidine and cyclohexane rings with two mirror image orientations of the phenyl and methoxyl groups. The calculations also indicate that the equilibrium conformations of the phenyl and methoxyl groups are very similar in the two diastereoisomers. A morphine-like conformation of the phenyl group was found to be very unfavorable because of a high barrier to rotation of the phenyl group. This does not have an apparent effect on opiate agonist properties, but does result in a significant weakening of the antagonist activity of the N-allyl derivative of α-azabicyclane. This is discussed in terms of a model for phenyl-axial and phenyl-equatorial opiate substrates which accounts for both similarities and differences in their structure–activity relationships. A detailed comparison is also made between the computed structures and those observed by x-ray crystallography with excellent agreement between the two.