Reproducibility of Biomolecular Corona Experiments: A Primer for Reliable Results

The biomolecular corona is a key component controlling the identity of nanomaterials in physiological environments. Studies aimed at identifying factors shaping the biomolecular corona have proliferated in the last decade but have been performed by research groups with different backgrounds. Efforts made within the scientific community to guarantee the reproducibility of experimental data have identified protocol standardization as an indispensable step for advancing knowledge in this arena. To contribute to fulfill this gap, here the relevance of interoperator variability in biomolecular corona studies and the benefits arising from automated systems usage are explored. Moreover, the role of molecular crowding during nanoparticle-biofluid incubation and the effect of washing the pellet during corona isolation are thoroughly investigated. It is believed that the findings will help researchers enhance the accuracy of experimental design and reporting.     

Birational aspects of the geometry of Varieties of Sums of Powers

Varieties of Sums of Powers describe the additive decompositions of a homogeneous polynomial into powers of linear forms. The study of these varieties dates back to Sylvester and Hilbert, but only few of them, for special degrees and number of variables, are concretely identified. In this paper we aim to understand a general birational behavior of VSP. To do this we birationally embed these varieties into Grassmannians and prove the rational connectedness of many VSP in arbitrary degrees and number of variables.     

Coordination properties of the multifunctional S,N,S zwitterionic ligand EtNHC(S)Ph2PNPPh2C(S)NEt

The reaction of trialkylphoshanes and amino-phosphanes with isothiocyanates yields adducts containing the zwitterionic thioamidyl-phosphonium P⁺C(S)N^? functional group. Ligands containing this group were not previously studied, probably due to their instability towards dissociation, in the presence of metal species able to coordinate the P atom. The ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt (HEtSNS) was obtained by reaction of Ph₂PNHPPh₂ with ethylisothiocyanate and proved to be very versatile: it can be protonated giving cation H₂EtSNS⁺ and deprotonated forming the dianion–cation EtSNS^?. HEtSNS and its derivatives behave as ligands showing five possible coordination fashions, S,N,S tridentate and S,S-bidentate (with a bite-angle varying from 180° to 90°), S-monodentate, S,S bridging and N,N,N interaction. Here we describe the coordination chemistry of HEtSNS, in particular towards Rh, Cu, Ag and Au, and some properties of its complexes which are still the only examples containing the P⁺C(S)N^? zwitterionic group.     

Synthesis and spectroscopic studies of the charge transfer complexes of 2- and 3-aminopyridine

The interactions of the electron donors 2-aminopyridine (2APY) and 3-aminopyridine (3APY) with the π-acceptors tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 2-chloro-1,3,5-trinitrobenzene (picryl chloride, PC), and 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil) were studied spectrophotometrically in chloroform at room temperature. The electronic and infrared spectra of the formed molecular charge transfer (CT) complexes were recorded. Photometric titration showed that the stoichiometries of the reactions were fixed and depended on the nature of both the donor and the acceptor. The molecular structures of the CT-complexes were, however, independent of the position of the amino group on the pyridine ring and were formulated as [(APY)(TCNE)], [(APY)(DDQ)], [(APY)(PC)], and [(APY) (chloranil)]. The formation constants (K_CT), charge transfer energy (E_CT) and molar extinction coefficients (_CT) of the formed CT-complexes were obtained.     

Young Integrals and SPDEs

In this note, we study the non-linear evolution problem $dY_t = -A Y_t dt + B(Y_t) dX_t,$ where $XIn this note, we study the non-linear evolution problem where is a -H?lder continuous function of the time parameter, with values in a distribution space, and the generator of an analytical semigroup. Then, we will give some sharp conditions on in order to solve the above equation in a function space, first in the linear case (for any value of in ), and then when satisfies some Lipschitz type conditions (for ). The solution of the evolution problem will be understood in the mild sense, and the integrals involved in that definition will be of Young type.     

A Numerical Approach to Copolymers at Selective Interfaces

We consider a model of a random copolymer at a selective interface which undergoes a localization/delocalization transition. In spite of the several rigorous results available for this model, the theoretical characterization of the phase transition has remained elusive and there is still no agreement about several important issues, for example the behavior of the polymer near the phase transition line. From a rigorous viewpoint non coinciding upper and lower bounds on the critical line are known. In this paper we combine numerical computations with rigorous arguments to get to a better understanding of the phase diagram. Our main results include:

On the number of Waring decompositions for a generic polynomial vector

We prove that a general polynomial vector $(f_1,f_2,f_3)$ in three homogeneous variables of degrees $(3,3,4)$ has a unique Waring decomposition of rank 7. This is the first new case we are aware of, and likely the last one, after five examples known since the 19th century and the binary case. We prove that there are no identifiable cases among pairs $(f_1,f_2)$ in three homogeneous variables of degree $(a,a+1)$, unless $a=2$, and we give a lower bound on the number of decompositions. The new example was discovered with Numerical Algebraic Geometry, while its proof needs Nonabelian Apolarity.     

Synthesis and Characterization of Novel Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties

The tetrabutylammonium (TBA⁺) salts of square‐planar monoanionic gold complexes of the unsymmetrically substituted Ar,H‐edt^2? 1,2‐dithiolene ligands (Ar,H‐edt^2?=arylethylene‐1,2‐dithiolato; Ar=phenyl ( 1 ^?), 2‐naphthyl ( 2 ^?), and 1‐pyrenyl ( 3 ^?)) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species ( 1 , 2 , and 3 , respectively) were obtained in CH₂Cl₂ solution at room temperature by diiodine oxidation. The single‐crystal X‐ray diffraction structural data collected for (TBA⁺)( 2 ^?), supported by DFT theoretical calculations, are consistent with the ene‐1,2‐dithiolate form of the ligand and the Au^III oxidation state. All complexes feature intense near‐IR absorptions (at about 1.5 μm) in their neutral states and Vis‐emitting properties in the 400–550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3 ^?/ 3 couple. The spectroscopic and electrochemical features of 1 ^x? and 2 ^x? (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time‐dependent (TD) DFT calculations.