Dynamic Interactions in Synthetic Receptors: A Guest Exchange Saturation Transfer Study

The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF₄⁻ are mediated by the side chains on the receptor (100 s⁻¹<k_ex<5000 s⁻¹), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method.     

On bulk-service MAP/PH L,N /1/N G-Queues with repeated attempts

We consider a retrial queue with a finite buffer of size N, with arrivals of ordinary units and of negative units (which cancel one ordinary unit), both assumed to be Markovian arrival processes. The service requirements are of phase type. In addition, a PH^L,N bulk service discipline is assumed. This means that the units are served in groups of size at least L, where 1≤ L≤ N. If at the completion of a service fewer than L units are present at the buffer, the server switches off and waits until the buffer length reaches the threshold L. Then it switches on and initiates service for such a group of units. On the contrary, if at the completion of a service L or more units are present at the buffer, all units enter service as a group. Units arriving when the buffer is full are not lost, but they join a group of unsatisfied units called “orbit”. Our interest is in the continuous-time Markov chain describing the state of the queue at arbitrary times, which constitutes a level dependent quasi-birth-and-death process. We start by analyzing a simplified version of our queueing model, which is amenable to numerical calculation and is based on spatially homogeneous quasi-birth-and-death processes. This leads to modified matrix-geometric formulas that reveal the basic qualitative properties of our algorithmic approach for computing performance measures. AMS Subject Classification: Primary 60K25 Secondary 68M20 90B22.     

Effect of pressure on the proton transfer rate from a photoacid to a solvent. 4. Photoacids in methanol

The pressure dependence of the excited-state proton dissociation rate constant of four photoacids, 2-naphthol-6,8-disulfonate (2N68DS), 10-hydroxycamptothecin (10-CPT), 5-cyano-2-naphthol (5CN2), and 5,8-dicyano-2-naphthol (DCN2), are studied in methanol. The results are compared with the results of the pressure dependence study we recently conducted for several photoacids in water, ethanol, and propanol. The pressure dependence is explained using an approximate stepwise two-coordinate proton transfer model. The increase in rate, as a function of pressure, manifests a strong dependence of proton tunneling on the distance which decreases with an increase of pressure between the two oxygen atoms involved in the process. The decrease in the proton transfer rate with increasing pressure reflects the dependence of the reaction on the solvent relaxation rate. We found that, for the relatively weak photoacids 2N68DS, 10-CPT, and 5CN2, the proton transfer rate constant increases by a factor of about 5-8 at a pressure of about 1.5 GPa. For a strong photoacid like DCN2, the rate increase was only by a factor of 2.     

Discrimination of guests encapsulation in large hexameric molecular capsules in solution: pyrogallol[4]arene versus resorcin[4]arene capsules

NMR experiments demonstrate that, although 2b and 3b form hexameric capsules in chloroform solutions and despite the very similar building units of these hexamers, 3b encapsulates only the noncharged trialkylamines while 2b can encapsulate both the noncharged trialkylamines and the respective ammonium salts obtained by the addition of DCl. In fact, it was found that protonation that forms in situ the ammonium salt ejects the guest from the hexameric capsule of 3b. This is a general observation as it was found for guests containing alkyl chains of four, five, six, and eight carbons.     

Convergence of intermediate rows of minimal polynomial and reduced rank extrapolation tables

Let {x _m} _m ^=0/ be a vector sequence obtained from a linear fixed point iterative technique in a general inner product space. In two previous papers [6,9] the convergence properties of the minimal polynomial and reduced rank extrapolation methods, as they are applied to the vector sequence above, were analyzed. In particular, asymptotically optimal convergence results pertaining to some of the rows of the tables associated with these two methods were obtained. In the present work we continue this analysis and provide analogous results for the remaining (intermediate) rows of these tables. In particular, when {x _m} _m ^=0/ is a convergent sequence, the main result of this paper says, roughly speaking, that all of the rows converge, and it also gives the rate of convergence for each row. The results are demonstrated numerically through an example.     

Reaction of acetylenes with transition metals: VIII. π-allylpalladium complexes from acetylenes and alkenes

Coupling of diarylacetylenes with alkenes in the presence of dichlorobis(benzonitrile)palladium gives chloro(syn-1-chloro-anti-1-aryl-syn-3-alkyl)-π-allylpalladium complexes.     

E ⊗ ϵ Jahn–Teller anharmonic coupling for an octahedral system

The coupling between doubly degenerate electronic states and doubly degenerate vibrations is analyzed for an octahedral system on the basis of the introduction of an anharmonic Morse potential for the vibronic part. The vibrations are described by anharmonic coherent states and their linear coupling with the electronic states is considered. The matrix elements of the vibronic interaction are built and the energy levels corresponding to the interaction Hamiltonian derived. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Structure of microemulsions with gemini surfactant studied by solvatochromic probe and diffusion NMR

The structure of microemulsions prepared by the anionic gemini surfactant didodecyl diphenyl ether disulfonate (C12-DADS) was investigated by a solvatochromic probe and nuclear magnetic resonance (NMR) diffusion measurements. The NMR measurements indicate the presence of bicontinuous and oil-in-water microemulsions depending on microemulsion composition. The absorbance spectra of the solvatochromic probe, Nile red, indicate the solubilization of the probe in different sites, in agreement with the NMR findings. It was also found that the microemulsions were capable of dissolving the hydrophobic probe, Nile red, up to four times better than expected if it were simply dissolved in the toluene phase.