Photoluminescence-Based Techniques for the Detection of Micro- and Nanoplastics

The growing numbers related to plastic pollution are impressive, with ca. 70 % of produced plastic (>350 tonnes/year) being indiscriminately wasted in the environment. The most dangerous forms of plastic pollution for biota and human health are micro- and nano-plastics (MNPs), which are ubiquitous and more bioavailable. Their elimination is extremely difficult, but the first challenge is their detection since existing protocols are unsatisfactory for microplastics and mostly absent for nanoplastics. After a discussion of the state of the art for MNPs detection, we specifically revise the techniques based on photoluminescence that represent very promising solutions for this problem. In this context, Nile Red staining is the most used strategy and we show here its pros and limitations, but we also discuss other more recent approaches, such as the use of fluorogenic probes based on perylene-bisimide and on fluorogenic hyaluronan nanogels, with the added values of biocompatibility and water solubility.     

Quantitative analysis of two-dimensional gel-separated proteins using isotopically marked alkylating agents and matrix-assisted laser desorption/ionization mass spectrometry

We describe a simple approach for the relative quantification of individual proteins within a mixture. The method is based on the differential labelling of the mixtures by use of a commercially available acrylamide and deuterium-labelled [2,3,3'-d(3)]-acrylamide to alkylate proteins prior to two-dimensional (2-D) gel electrophoresis. The tryptic digests of the separated proteins were subjected to reflector matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) analysis and the relative peak heights of cysteine-containing peptides were used to quantify their precursor proteins. This approach was tested for the relative quantification of proteins within an artificial mixture of standard proteins and for proteins observed in a 2-D map of rat serum. A good correlation was found between the measured ratios derived from MALDI-TOF data and those theoretically calculated prior to 2-D analysis via known mixing ratios of the two alkylating reagents. The described procedure has proved to be effective for comparative measurements of protein abundances within the investigated mixtures.     

Spectral properties and absolute rate constants for beta-scission of ring-substituted cumyloxyl radicals. A laser flash photolysis study

A laser flash photolysis study of the spectral properties and beta-scission reactions of a series of ring-substituted cumyloxyl radicals has been carried out. All cumyloxyl radicals display a broad absorption band in the visible region of the spectrum, which decays on the microsecond time scale, leading to a strong increase in absorption in the UV region of the spectrum, which is attributed to the corresponding acetophenone formed after beta-scission of the cumyloxyl radicals. The position of the visible absorption band is red-shifted by the presence of electron-donating ring substituents, while a blue-shift is observed in the presence of electron-withdrawing ring substituents, suggesting that + R ring substituents promote charge separation in the excited cumyloxyl radical through stabilization of the partial positive charge on the aromatic ring of an incipient radical zwitterion. Along this line, an excellent Hammett-type correlation between the experimentally measured energies at the visible absorption maxima of the cumyloxyl radicals and sigma(+) substituent constants is obtained. A red-shift is also observed on going from MeCN to MeCN/H(2)O for all cumyloxyl radicals, pointing toward a specific effect of water. The ring substitution does not influence to a significant extent the rate constants for beta-scission of the cumyloxyl radicals, which varies between 7.1 x 10(5) and 1.1 x 10(6) s(-1), a result that suggests that cumyloxyl radical beta-scission is not governed by the stability of the resulting acetophenone. Finally, k(beta) increases on going from MeCN to the more polar MeCN/H(2)O 1:1 for all cumyloxyl radicals, an observation that reflects the increased stabilization of the transition state for beta-scission through increased solvation of the incipient acetophenone product.     

Allylation of exocyclic N-Acyliminium ions generated from chiral N-[1-(phenylsulfonyl)alkyl]oxazolidin-2-ones

N-[1-(Phenylsulfonyl)alkyl]oxazolidin-2-ones are successfully prepared by condensation of the corresponding optically active oxazolidin-2-ones with aldehydes and benzenesulfinic acid. At low temperature, in the presence of titanium tetrachloride, these sulfones are converted into N-acyliminium ions, which react with allyltrimethylsilane with a variable degree of stereoselectivity. The best results are obtained with (R)-5,5-dimethyl-4-phenyloxazolidin-2-one as a chiral auxiliary. Cleavage of the oxazolidin-2-one ring with lithium/ammonia affords the corresponding homoallylamines, which reveal an absolute configuration opposite that expected on the basis of the usual steric effects. A complexation of the Lewis acid with the N-acyliminium ion may be responsible of this rather unusual stereochemical outcome.     

Uncertainty Inequalities for Fourier Series of Pairs of Reciprocal Positive Functions

In the early 1930s, Wiener proved that if f(x) is a strictlypositive periodic function whose Fourier series is absolutelyconvergent, then the Fourier series of g(x)=1/f(x) is also absolutelyconvergent [8, pp. 10–14]. This phenomenon can be easilyunderstood nowadays using Banach algebra techniques (see, forexample, [4, pp. 202–203]). In fact, these techniquesallow us to study the absolute convergence of g(x)=F(f(x)),where F is holomorphic in an open subset of C that containsthe range of f(x) (for xR). In this context, Wiener's originalproblem corresponds to the choice F(z)=1/z. In this work we want to analyse the constraints on the simultaneousrate of vanishing of the Fourier coefficients f(n) and (n) asn. We shall focus on g=1/f, but we shall also study the generalcase g=F(f). In either case, there are obviously no constraintswhen f is a constant function. Although this problem does not seem to be directly related touncertainty inequalities for the Fourier Transform, we observethat there are some analogies, both in the nature of the resultsand in the proof techniques. The general fact with which weare dealing is that f(n) and (n) cannot vanish too quickly atthe same time as n, unless f(x) is constant. The general factthat underlies uncertainty inequalities is that a non-periodicfunction (x) and its Fourier Transform circ;(u) cannot vanishtoo quickly at the same time as x and u, unless (x) is zero(almost everywhere). For a simple introduction to some aspectsof uncertainty inequalities, see [5]; for a thorough and recentintroduction to this vast subject, see [3]. 1991 MathematicsSubject Classification 42A05, 42A16, 42A99.     

A speciality theorem for Cohen-Macaulay space curves

We prove a version of the Halphen Speciality Theorem for locally Cohen-Macaulay curves in . To prove the theorem, we strengthen some results of Okonek and Spindler on the spectrum of the ideal sheaf of a curve. As an application, we classify curves having index of speciality as large as possible once we fix the degree of and the minimum degree of a surface containing .

     

Space tensors in general relativity II: Physical applications

The general theory of space tensors is applied to the study of a space-time manifoldsV ₄ carrying a distinguished time-like congruence Γ. The problem is to determine a physically relevant spatial tensor analysis over (V ₄, Γ), in order to proceed to a correct formulation of Relative Kinematics and Dynamics. This is achieved by showing that each choice of gives rise to a corresponding notion of ‘frame of reference’ associated with the congruence Γ. In particular, the frame of reference (Γ, ∇*) determined by the standard spatial tensor analysis is shown to provide the most natural generalization of the concept of frame of reference in Classical Physics. The previous arguments are finally applied to the study of geodesic motion inV ₄. As a result, the general structure of the gravitational fields in the frame of reference (Γ, ∇*) is established. This work was assisted by funds from the C.N.R. under the aegis of the activity of the National Group for Mathematical Physics.     

On the renormalization method: a different outlook,and the energy-momentum tensor in the gφ4 theory

An alternate method of renormalizing a quartic self-interacting boson theory has been developed. We find that one can obtain finite renormalized expressions for the perturbation theory contributions to the Green's function without carrying out limiting procedures. As a consequence of the analysis, one is able to renormalize explicitly the field energy-momentum tensor to all orders. There exists a one-parameter family of renormalized tensors. The method will allow for a simple determination of the asymptotic “zero-mass” theory.