Harnessing the enantiomeric recognition ability of hydrophobic polymers of intrinsic microporosity (PIM-1) toward amino acids by converting them into hydrophilic polymer dots
JOURNAL OF MATERIALS CHEMISTRY C
Authors: Feizi, Froozan; Shamsipur, Mojtaba; Gholivand, Mohammad Bagher; Taherpour, Avat (Arman); Barati, Ali; Shamsipur, Hosna; Mohajerani, Ezeddin; Budd, Peter
Abstract
In this work, we synthesized novel polymer dots (Pdots) from polymers of intrinsic microporosity (PIM-1) containing a racemic mixture ofR- andS-chiral centers as the hydrophobic conjugated polymer chains. AlthoughPIM-1showed no enantiomeric recognition abilities toward amino acids, we found that this ability can emerge after converting these hydrophobic polymers into nanosized water-soluble Pdots, using poly(styrene-co-maleic anhydride) (PSMA) as a co-polymer that provides carboxyl functional groups on the surface of the Pdots. The stronger interaction of Pdots with amino acids and their higher ability to discriminate the amino acid enantiomers were clearly confirmed by the quantum mechanical calculations, where the difference between the calculated energies for the interaction ofd- andl-amino acid enantiomers with the simulated Pdots were remarkably higher than those obtained for the interaction of the enantiomers with justPIM-1. Indeed, the carboxyl surface groups of Pdots played a critical hook-like role in bringing the amino acid enantiomers and chiral centers of the embeddedPIM-1closer together to provide more efficient interactions. The synthesized Pdots were successfully used as highly efficient chiral probes for chiral recognition and determination of the enantiomers of (Phe), tryptophan (Trp), and tyrosine (Tyr) as samples by both fluorescence and circular dichroism spectroscopic methods. The results of this study demonstrated the potential of the suggested method to utilize hydrophobic chiroptical probes in enantiomeric recognition of hydrophilic chiral species.
Protein tyrosine phosphatase receptor type Q in cerebrospinal fluid reflects ependymal cell dysfunction and is a potential biomarker for adult chronic hydrocephalus
EUROPEAN JOURNAL OF NEUROLOGY
Authors: Nakajima, M.; Rauramaa, T.; Makinen, P. M.; Hiltunen, M.; Herukka, S. -K.; Kokki, M.; Musialowicz, T.; Jyrkkanen, H. -K.; Danner, N.; Junkkari, A.; Koivisto, A. M.; Jaaskelainen, J. E.; Miyajima, M.; Ogino, I.; Furuta, A.; Akiba, C.; Kawamura, K.; Kamohara, C.; Sugano, H.; Tange, Y.; Karagiozov, K.; Leinonen, V.; Arai, H.
Abstract
Background and purpose Protein tyrosine phosphatase receptor type Q (PTPRQ) was extracted from the cerebrospinal fluid (CSF) of patients with probable idiopathic normal-pressure hydrocephalus (iNPH) by proteome analysis. We aimed to assess the feasibility of using CSF PTPRQ concentrations for the additional diagnostic criterion of iNPH in Japanese and Finnish populations. Methods We compared PTPRQ concentrations among patients with probable iNPH and neurologically healthy individuals (normal control [NC] group), patients with normal-pressure hydrocephalus (NPH) of acquired and congenital/developmental aetiologies, patients with Alzheimer's disease and patients with Parkinson's disease in a Japanese analysis cohort. A corresponding iNPH group and NC group in a Finnish cohort was used for validation. Patients in the Finnish cohort who underwent biopsy were classified into two groups based on amyloid and/or tau deposition. We measured PTPRQ expression levels in autopsied brain specimens of iNPH patients and the NC group. Results Cerebrospinal fluid PTPRQ concentrations in the patients with NPH of idiopathic, acquired and congenital/developmental aetiologies were significantly higher than those in the NC group and those with Parkinson's disease, but iNPH showed no significant differences when compared with those in the Alzheimer's disease group. For the patients with iNPH, the area under the receiver-operating characteristic curve was 0.860 in the Japanese iNPH and 0.849 in the Finnish iNPH cohorts. Immunostaining and in situ hybridization revealed PTPRQ expression in the ependymal cells and choroid plexus. It is highly possible that the elevated PTPRQ levels in the CSF are related to ependymal dysfunction from ventricular expansion. Conclusions Cerebrospinal fluid PTPRQ levels indicated the validity of this assay for auxiliary diagnosis of adult chronic hydrocephalus.