Sequence Analysis for Alternating Copolymers by MALDI‐TOF‐MS: Importance of Initiator Selectivity for Comonomer Pair

A special initiator for metal‐catalyzed living radical polymerization facilitates sequence analyses by matrix‐assisted laser desorption/ionization time of flight mass spectrometry (MALDI‐TOF‐MS) of alternating copolymers from styrene and maleimide derivatives. The initiator is a malonate‐based alkyl halide (DEMM‐Br), in which two ester groups are attached on the carbon neighboring to bromide, and poor electron density of the radical species allows determination of next unit to the initiator in resultant alternating copolymers due to the selective initiation to styrene derivative. Thanks to the well‐defined α‐end group, sequence of the oligomeric products via radical copolymerization of PMS and EMI with DEMM‐Br can be more simply analyzed by MALDI‐TOF‐MS, and indeed the following are clarified: the crossover propagation is almost perfectly controlled regardless of the injection ratio; a minor error event of the disordered alternating sequence containing St–St sequential unit could take place; the minor error can be suppressed with an excess amount of maleimide.

     

Unprecedented Sequence Control and Sequence‐Driven Properties in a Series of AB‐Alternating Copolymers Consisting Solely of Acrylamide Units

Herein, we report a method to synthesize a series of alternating copolymers that consist exclusively of acrylamide units. Crucial to realizing this polymer synthesis is the design of a divinyl monomer that contains acrylate and acrylamide moieties connected by two activated ester bonds. This design, which is based on the reactivity ratio of the embedded vinyl groups, allows a “selective” cyclopolymerization, wherein the intramolecular and intermolecular propagation are repeated alternately under dilute conditions. The addition of an amine to the resulting cyclopolymers afforded two different acryl amide units, i.e., an amine‐substituted acryl amide and a 2‐hydroxy‐ethyl‐substituted acryl amide in alternating sequence. Using this method, we could furnish ten types of alternating copolymers; some of these exhibit unique properties in solution and in the bulk, which are different from those of the corresponding random copolymers, and we attributed the differences to the alternating sequence.     

Monitoring of metabolic profiling and water status of Hayward kiwifruits by nuclear magnetic resonance

The metabolic profiling of kiwifruit (Actinidia deliciosa, Hayward cultivar) aqueous extracts and the water status of entire kiwifruits were monitored over the season (June-December) using nuclear magnetic resonance (NMR) methodologies. The metabolic profiling of aqueous kiwifruit extracts was investigated by means of high field NMR spectroscopy. A large number of water-soluble metabolites were assigned by means of 1D and 2D NMR experiments. The change in the metabolic profiles monitored over the season allowed the kiwifruit development to be investigated. Specific temporal trends of aminoacids, sugars, organic acids and other metabolites were observed.The water status of kiwifruits was monitored directly on the intact fruit measuring the T₂ spin-spin relaxation time by means of a portable unilateral NMR instrument, fully non-invasive. Again, clear trends of the relaxation time were observed during the monitoring period.The results show that the monitoring of the metabolic profiling and the monitoring of the water status are two complementary means suitable to have a complete view of the investigated fruit.     

Spontaneous alternating copolymerization of isobutoxyallene with 4-phenyl-1,2,4-triazoline-3,5-dione

The spontaneous copolymerization of isobutoxyallene ( 1 ) with 4-phenyl-1,2,4-triazoline-3,5-dione ( 2 ) was carried out to afford a copolymer with a number-average molecular weight of 5900–10,300. The copolymer consisted of a 2,3-polymerization unit of 1 and a  NN polymerization unit of 2 , maintaining an alternating character regardless of the monomer feed ratio. The corresponding copolymerization of 1 with 2 in the presence of methanol afforded the adduct of the compounds without the polymer, indicating the generation of a zwitterion of 1 and 2 . © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1564–1571, 2001     

Analysis of Alternating-Priority Queueing Models with (Cross) Correlated Switchover Times

This paper analyzes a single server queueing system in which service is alternated between two queues and the server requires a (finite) switchover time to switch from one queue to the other. The distinction from classical results is that the sequence of switchover times from each of the queues need not be i.i.d. nor independent from each other; each sequence is merely required to form a stationary ergodic sequence. With the help of stochastic recursive equations explicit expressions are derived for a number of performance measures, most notably for the average delay of a customer and the average queue lengths under different service disciplines. With these expressions a comparison is made between the service disciplines and the influence of correlation is studied. Finally, through a number of examples it is shown that the correlation can significantly increase the mean delay and the average queue lengths indicating that the correlation between switchover times should not be ignored. This has important implications for communication systems in which a common communication channel is shared amongst various users and where the time between consecutive data transfers is correlated (for example in ad-hoc networks). In addition to this a number of notational mistakes in well-known existing literature are pointed out. AMS subject classification: 68M20, 60J85 A shorter version of this work has been published in the proceedings of IEEE Infocom 2005. This work was partly sponsored by the EURONGI network of excellence.     

Spatial structure and energy spectrum of ion beams studied with CN detectors within a small PF device

The paper reports the application of Solid-State Nuclear Track Detectors to study the pulsed plasma-ion streams emitted from plasma-focus (PF) type discharges, which were performed within a low-energy PACO device constructed at Instituto de Fisica Arroyo Seco. The PACO device was operated under static initial gas conditions or with dynamic gas puffing. Studies of the structure of the fast deuteron beams were carried out within an energy range from 80 keV to about 2 MeV. Studies of ion energy and an ion angular distribution were also performed. The measurements showed that the fast deuterons are emitted in many “narrow” micro-beams, as in other larger PF devices. The anisotropy of the deuteron angular distribution was explained by the stochastic character of the formation of local ion sources within the PF discharge column.     

Plasma focus based flash hard X-ray source in the 100 keV region with reproducible spectrum

A pulsed hard X-ray source with shot to shot reproducible spectrum, based on a 4.7 kJ small-chamber Mather-type plasma focus device, is presented. The hard X-ray output spectrum was measured in a single shot basis by differential absorption on metallic plates. The measured spectra have a single dominant peak around 75 keV and a spectral bandwidth covering the 40-150 keV range. A hard X-ray dose of (53±3) μGy per shot was measured on axis at 53 cm from the source, and found to be uniform within a half aperture angle of 6°.     

On large sets of almost Hamilton cycle decompositions

A large set of CS(v, k, λ), k‐cycle system of order v with index λ, is a partition of all k‐cycles of K_v into CS(v, k, λ)s, denoted by LCS(v, k, λ). A (v ? 1)‐cycle is called almost Hamilton. The completion of the existence spectrum for LCS(v, v ? 1, λ) only depends on one case: all v ≥ 4 for λ = 2. In this article, it is shown that there exists an LCS(v, v ? 1,2) for any v ≡ 0,1 (mod 4) except v = 5, and for v = 6,7,10,11. © 2006 Wiley Periodicals, Inc. J Combin Designs 16: 53–69, 2008     

Anionic alternating copolymerization behavior of bifunctional six‐membered lactone and glycidyl phenyl ether

A copolymerization of 10‐methyl‐2H,8H‐benzo‐[1,2‐b:5,4‐b′]bipyran‐2,8‐dione ( 1 ) and glycidyl phenyl ether (GPE) was studied. 1 was a bislactone designed as a bifunctional analogue of 3,4‐dihydrocoumarin (DHCM), of which anionic 1:1 alternating copolymerization with GPE has been reported by us, previously. This alternating nature was inherited by the present copolymerization of 1 and GPE, leading to an intriguing copolymerization behavior in contrast to the ordinary statistical copolymerizations of monofunctional monomers and bifunctional monomers usually controlled by the proportional dependence of the crosslinking density on the monomer feed ratio: (1) When the feed ratio [GPE]₀/[ 1 ]₀ was 1, the two monomers underwent the 1:1 alternating copolymerization. In this case, 1 behaved as a monofunctional monomer, that is, only one of the two lactones in 1 participated in the copolymerization allowing the other lactone moiety to be introduced into the side chain almost quantitatively. (2) Increasing the feed ratio [GPE]₀/[1]₀ to larger than 4 allowed almost all of the lactone moieties to participate in the copolymerization system to give the corresponding networked polymers efficiently. The compositions of the copolymers [GPE unit]/[ 1 ‐derived acyclic ester unit] were always biased to smaller values than the feed ratios [GPE]₀/[lactone moiety in 1 ]₀ by the intrinsic 1:1 alternating nature of the copolymerization. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3662–3668, 2009     

Determination of depth-of-focus in lensless in-line digital particle holography

Lensless in-line digital particle holography (DPH) can be thought of as a special case of photography, and its depth of focus (DoF) characteristics combine those of both photography and holography. The effect of important parameters such as the pixel size and the number of pixels in a charge-coupled device (CCD), the object's distance, the wavelength of the laser, and the particle diameter on the DoF of a reconstruction image in lensless in-line DPH was investigated using simulation holograms. The DoF is directly proportional to the object distance and the particle size. As the wavelength of the laser increases, the DoF decreases. The DoF is inversely proportional to the pixel size and to the number of pixels in a CCD. Instead of expressing nonspecific proportional relationships for DoF, the DoF prediction equations for typical CCD cameras were obtained using DoF data from many simulation holograms and efficient data-fitting software. Finally, the DoF prediction equations were verified using real holograms from a calibration target for several cases. Good agreement between measured and predicted values was confirmed.