Polycondensed nitrogen heterocycles. Part 21. Complete 13C NMR assignment of annelated phenanthridines

Two-dimensional nmr techniques were used for the complete assignment of ¹³C nmr spectra of pyrrolo-[1,2-f]-, pyrazolo[1,5-f]-, and 1,2,4-triazolo[1,5-f]phenanthridines.     

A "jellyfish" shaped green emitting gallium(III)-containing metallomesogen

The synthesis of the first gallium(III)-based liquid crystal has been achieved grafting around the metal centre two chelating 2-methylquinolin-8-olate anions and one monodentate 3,4,5-tris(hexadecyloxy)benzoyloxy ligand, allowing the resulting complex to be a soft luminescent material with the typical high quantum yield of pentacordinated gallium species.     

Use of a variably sensitive selected reaction monitoring method to extend the linear dynamic range for quantitative high-performance liquid chromatography/tandem mass spectrometry

A method has been devised with the capacity to extend the linear dynamic range of a triple quadrupole mass spectrometer operated in the selected reaction monitoring (SRM) mode of analysis. This extended range experiment can be realized by simultaneously acquiring variably sensitive data, via collision energy adjustment, for the same precursor-to-product ion transition within a single SRM method. While this method can be applied universally to many different study types without any detrimental effect to the analysis or throughput, it was applied herein to acquire and quantify, within a single analysis, the concentrations of GSK-A in a multiple-dose rodent study, that previously required a dilution scheme. Using this methodology, the linear dynamic range of GSK-A was increased over traditional methods by nearly two orders of magnitude, from 2.00-10,000 ng/mL to 0.500-100,000 ng/mL.     

8-hydroxyquinoline monomer, water adducts, and dimer. Environmental influences on structure, spectroscopic properties, and relative stability of cis and trans conformers

The low fluorescence quantum yield of 8-hydroxyquinoline cannot be correctly interpreted without knowing the form that such a compound assumes in different environments. The commonly accepted emission-quenching excited-state proton transfer can follow different reaction paths if 8-hydroxyquinoline is dimeric or monomeric or if it exists in the form of cis and trans conformers; in this light, the knowledge of the compound form in a particular environment is basic. We have performed a spectroscopic and computational investigation aimed at the determination of the form of 8-hydroxyquinoline in different solvents. UV-vis, fluorescence, and IR spectral features have been assigned by ab initio computations based on the density functional theory and time-dependent density functional theory; the density functional theory and MP2 computations have been applied to the determination of the relative stability of the dimeric and monomeric cis and trans forms of 8-hydroxyquinoline in different solvents. Molecular dynamics computations have been used to determine the compound behavior in water solutions. According to our results, 8-hydroxyquinoline shows a clear preference for the cis conformation (as dimer or monomer), but, in water solutions, a small fraction of the trans conformation is also present.     

Integratomics of Human Dermal Fibroblasts Treated with Low Molecular Weight Hyaluronic Acid

Hyaluronic acid (HA) is a glycosaminoglycan very common in commercial products from pharmaceuticals to cosmetics due to its widespread distribution in humans and its diversified physico-chemical proprieties. Despite its extended use and preliminary evidence showing even also opposite activities to the native form, the precise cellular effects of HA at low-molecular-weight (LWM-HA) are currently unclear. The ‘omics sciences currently in development offer a new and combined perspective on the cellular and organismal environment. This work aims to integrate lipidomics analyses to our previous quantitative proteomics one for a multi-omics vision of intra- and extra-cellular impact of different concentrations (0.125, 0.25, and 0.50%) of LMW-HA (20–50 kDa) on normal human dermal fibroblasts by LC-high resolution mass spectrometry (LC-HRMS). Untargeted lipidomics allowed us to identify 903 unique lipids mostly represented by triacylglycerols, ceramides, and phosphatidylcholines. According to proteomics analyses, LMW-HA 0.50% was the most effective concentration also in the lipidome rearrangement especially stimulating the synthesis of ceramides involved in skin hydration and reparation, cell signaling, and energy balance. Finally, integrative analyses showed 25 nodes covering several intra- and extra-cellular functions. The more complete comprehension of intra- and extra-cellular effects of LMW-HA here pointed out will be useful to further exploit its features and improve current formulations even though further studies on lipids biosynthesis and degradation are necessary.     

Polycondensed nitrogen heterocycles. Part 24. Pyrrolo[3,4-c]isoquinolinone by thermal rearrangement of a pyrrolylbenzotriazinone

Rearrangement under acidic conditions of the pyrrolylbenzotriazinone 7 afforded the pyrrolylbenzamides 10 and 11 . By thermal rearrangement instead, the first fully aromatic derivative of the pyrrolo[3,4-c]isoquinoline ring system 9 was obtained.     

Synthesis of derivatives of pyrazolo[1,5-a]pyrrolo[1,2-c][1,3,6]-benzotriazocine,a new class of compounds with potential CNS activity

The synthesis of derivatives of pyrazolo[1,5-a]pyrrolo[1,2-c][1,3,6]benzotriazocine was obtained by the reaction of arylaldehydes with some 1-(2-aminophenyl)-5-(pyrrol-1-yl)pyrazoles, as hydrochlorides. Characterization of this new class of compounds was effected with ir, pmr and ¹³C nmr spectral data.     

On the power of interaction

LetIP[f(n)] be the class of languages recognized by interactive proofs withf(¦x¦) interactions. Babai [2] showed that all languages recognized by interactive proofs with a bounded number of interactions can be recognized by interactive proofs with only two interactions; i.e., for every constantk, IP[k] collapses toIP[2].In this paper, we give evidence that interactive proofs with an unbounded number of interactions may be more powerful than interactive proofs with a bounded number of interactions. We show that for any polynomially bounded polynomial time computable functionf(n) and anyg(n)=o(f(n)) there exists an oracleB such thatIP ^B [f(n)] ₌ IP ^B [g(n)].The techniques employed are extensions of the techniques for proving lower bounds on small depth circuits used in [6], [14] and [10].Research done while in the Department of Mathematics at M. I. T. and supported by an ONR graduate fellowship.Supported in part by NSF Grant DCR MCS8509905.Research done while at the Laboratory for Computer Science at M. I. T. and Supported by an IBM fellowship.     

Competitive queue policies for differentiated services

We consider the setting of a network providing differentiated services. As is often the case in differentiated services, we assume that the packets are tagged as either being a high priority packet or a low priority packet. Outgoing links in the network are serviced by a single FIFO queue.Our model gives a benefit of α1 to each high priority packet and a benefit of 1 to each low priority packet. A queue policy controls which of the arriving packets are dropped and which enter the queue. Once a packet enters the queue it is eventually sent. The aim of a queue policy is to maximize the sum of the benefits of all the packets it sends.We analyze and compare different queue policies for this problem using the competitive analysis approach, where the benefit of the online policy is compared to the benefit of an optimal offline policy. We derive both upper and lower bounds for the policies we consider. We believe that competitive analysis gives important insight to the performance of these queuing policies.     

The Arrow of Time: From Universe Time-Asymmetry to Local Irreversible Processes

In several previous papers we have argued for a global and non-entropic approach to the problem of the arrow of time, according to which the “arrow” is only a metaphorical way of expressing the geometrical time-asymmetry of the universe. We have also shown that, under definite conditions, this global time-asymmetry can be transferred to local contexts as an energy flow that points to the same temporal direction all over the spacetime. The aim of this paper is to complete the global and non-entropic program by showing that our approach is able to account for irreversible local phenomena, which have been traditionally considered as the physical origin of the arrow of time.