Mass‐Spectrometric Observation of Counter Anion Production in SU‐8 Exposed to UV Light and its Use for Dill C Parameter Determination

Photopolymerization is a phenomenon that is the basis of much of today's microfabrication technology and intense research is conducted to improve its control and the characteristics of end products for a variety of applications. The design of microscopic structures often relies on the accurate knowledge and modeling of photopolymer's behavior upon exposure, i.e. the Dill parameters, for each radiation species of interest and therefore the development of flexible characterization techniques is of great importance. SU‐8 is a popular compound that is representative of a whole class that relies on cationic polymerization, where an acid is obtained via photolysis of an onium salt during exposure. Here we report on the observation of SbF₆^? via laser desorption mass spectrometry on SU‐8 exposed to UV light at the wavelength of 365 nm and demonstrate that the yield of this counter‐anion as a function of exposure is consistent with the Dill C parameter value available in the literature. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 967–972     

Surface modification of polyamide 12 angioplasty balloons by photochemical reaction with an aromatic azide

Polyamide 12 (PA12) is used in a variety of applications when low moisture absorption, good dimensional stability, and toughness are required. Polyamide 12 is one of the polymers most frequently employed to fabricate angioplasty balloon catheters; however, its high hydrophobicity and chemical inertness require the application of coatings to make its surface more hydrophilic and biocompatible. In this work, an alternative method, based on the photochemical reaction of PA12 with a hydrophilic aromatic azide, was developed. Static and dynamic contact angle measurements evidenced that the surface modification process was able to improve PA12 wettability and that the effects were retained even after 12 months from surface treatment. Polyamide 12 modification resulted in an increase of its surface free energy, as evaluated by the van Oss, Good, and Chaudhury method. X‐ray photoelectron spectroscopy confirmed the presence of the aromatic azide on PA12 surface. Finally, compliance tests showed that the modification process did not reduce the mechanical performance of balloons.     

Reducing the computational cost of NMR crystallography of organic powders at natural isotopic abundance with the help of 13C-13C dipolar couplings

Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed ¹H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using ¹³C-¹³C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although ¹³C-¹³C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.     

MCRs reshaped into a switchable microwave-assisted protocol toward 5-aminoimidazoles and dihydrotriazines

A tunable microwave-assisted protocol for the synthesis of two biologically relevant families of heterocycles has been designed. Via a simple switch of reaction conditions, the same starting materials can be engaged in either an improved synthesis of the dihydrotriazine scaffold or a novel, first-in-class MCR to render the challenging 5-aminoimidazole nucleus in a single step. An additional first-in-class MCR is also reported utilizing guanidines to afford 2,5-aminoimidazoles.     

Synthesis and Biological Evaluation of RGD Peptidomimetic–Paclitaxel Conjugates Bearing Lysosomally Cleavable Linkers

Two small‐molecule–drug conjugates (SMDCs, 6 and 7 ) featuring lysosomally cleavable linkers (namely the Val–Ala and Phe–Lys peptide sequences) were synthesized by conjugation of the α_vβ₃‐integrin ligand cyclo[DKP–RGD]‐CH₂NH₂ ( 2 ) to the anticancer drug paclitaxel (PTX). A third cyclo[DKP–RGD]–PTX conjugate with a nonpeptide “uncleavable” linker ( 8 ) was also synthesized to be tested as a negative control. These three SMDCs were able to inhibit biotinylated vitronectin binding to the purified α_Vβ₃‐integrin receptor at nanomolar concentrations and showed good stability at pH 7.4 and pH 5.5. Cleavage of the two peptide linkers was observed in the presence of lysosomal enzymes, whereas conjugate 8 , which possesses a nonpeptide “uncleavable” linker, remained intact under these conditions. The antiproliferative activities of the conjugates were evaluated against two isogenic cell lines expressing the integrin receptor at different levels: the acute lymphoblastic leukemia cell line CCRF‐CEM (α_Vβ₃?) and its subclone CCRF‐CEM α_Vβ₃ (α_Vβ₃+). Fairly effective integrin targeting was displayed by the cyclo[DKP–RGD]–Val–Ala–PTX conjugate ( 6 ), which was found to differentially inhibit proliferation in antigen‐positive CCRF‐CEM α_Vβ₃ versus antigen‐negative isogenic CCRF‐CEM cells. The total lack of activity displayed by the “uncleavable” cyclo[DKP–RGD]–PTX conjugate ( 8 ) clearly demonstrates the importance of the peptide linker for achieving the selective release of the cytotoxic payload.     

Entropy for Symbolic Dynamics with Overlapping Alphabets

We consider shift spaces in which elements of the alphabet may overlap nontransitively. We define a notion of entropy for such spaces and show that it is equal to a limit of entropies of standard (non-overlapping) shifts when the underlying shift is of finite type. When a shift space with overlaps arises as a model for a discrete dynamical system with a finite set of overlapping neighborhoods, the entropy gives a lower bound for the topological entropy of the dynamical system.     

A support for the identification of non-tryptic peptides based on low resolution tandem and sequential mass spectrometry data: The INSPIRE software

A simple software, to be used as an aid in the identification of non-tryptic peptides based on low resolution (3D-ion trap) tandem (MS/MS) and sequential (MS³) mass spectrometry data, is presented.