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Molecular Imprinting Technology for Biomimetic Assemblies

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Molecular Imprinting Technology for Biomimetic Assemblies N. Bereli et al./Hacettepe J. Biol. & Chem., 2020, 48 (5), 575-601 Hacettepe Journal of Biology and Chemistry Review Article journal homepage: www.hjbc.hacettepe.edu.tr Molecular Imprinting Technology for Biomimetic Assemblies Biomimetik Sistemler için Moleküler Baskılama Teknolojisi Nilay Bereli , Semra Akgönüllü , Sevgi Aslıyüce , Duygu Çimen , Ilgım Göktürk , Deniz Türkmen , Handan Yavuz and Adil Denizli* Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey. ABSTRACT he term biomimetic can be simply defined as the examination of nature. The scientist inspired from the enormous diversity Tof nature to solve human problems or facilitate the daily life by mimicking natural models, systems and elements especially in biomedical and therapeutic applications to make better drugs, artificial organs, sensing instruments etc. Biological recognition elements like proteins, antibodies, enzymes, DNA, lectins, aptamers, cells and viruses have been heavily used to ensure specificity in such applications in spite of their lack of stability and reusability. However, in the last two decades molecularly imprinted polymers, MIPs, have been synthesized as an alternative to mimic natural biological interactions for a broad spectrum of templates by means of coordinating functional monomers around template in the presence of cross- linker. This review will outline the broad contours of biomimetics prepared by molecular imprinting techniques and their practical applications in the separation techniques, tissue engineering applications, biomimetic surfaces, sensors, artificial membranes and drug delivery systems. Key Words Molecular imprinting, biomimetic, separation, sensing, polymer brushes, artificial membranes, drug delivery, tissue engineering. ÖZ iyomimetik terimi, kısaca doğanın incelenmesi olarak tanımlanabilir. Bilim adamları biyomedikal ve terapötik Buygulamalarda, daha iyi ilaçlar, yapay organlar, algılama aletleri vb. yapmak için doğal modelleri, sistemleri ve unsurları taklit ederek, insan sorunlarını çözmek ve günlük yaşamı kolaylaştırmak için doğanın muazzam çeşitliliğinden ilham aldılar. Bu tür uygulamalarda, stabilite ve tekrar kullanılabilirlikteki eksikliklere rağmen, özgüllüğü sağlamak için proteinler, antikorlar, enzimler, DNA, lektinler, aptamerler, hücreler ve virüsler gibi biyolojik tanıma öğeleri yoğun olarak kullanılmıştır. Bununla birlikte, son yirmi yılda moleküler baskılanmış polimerler (MIP’ler), çapraz bağlayıcının varlığında kalıp yapı etrafında fonksiyonel monomerlerin koordine edilmesi yoluyla geniş bir örnek yelpazesi oluşturmuş ve doğal biyolojik etkileşimleri taklit etmeye bir alternatif olarak sentezlenmiştir. Bu derleme, ayırma tekniklerinde, doku mühendisliği uygulamalarında, biyomimetik yüzeylerde, sensörlerde, yapay membranlar ve ilaç taşınım sistemlerinde moleküler baskılama teknikleriyle hazırlanan biyomimetiklerin genel hatlarını ve pratik uygulamalarını özetleyecektir. Anahtar Kelimeler Moleküler bakılama, biomimetik, ayırma, analiz, polimer fırçalar, yapay membranlar, ilaç salınımı, doku mühendisliği. Article History: Received: Sep 20, 2020; Revised: Sep 29, 2020; Accepted: Oct 20, 2020; Available Online: Oct 20, 2020. DOI: https://doi.org/10.15671/hjbc.801427 Correspondence to: A. Denizli, Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey. E-Mail: [email protected] 576 N. Bereli et al. / Hacettepe J. Biol. & Chem., 2020, 48 (5), 575-601 INTRODUCTION [4]. Dickey modified silica materials with some organic dyes including methyl orange and its homologs, by aci- he life is mainly based on a crucial term: molecular difying silica solutions of these dyes in to produce selec- Trecognition. Various functions of living systems, such tive adsorbents. When we come to the 1970s, Wulff et as enzymes, proteins, antibodies, nucleic acids and cell al. introduced the main concept of molecular imprinting signaling actualize via molecular recognition. Molecu- technology which is still valid today [5]. This approach lar recognition consists of the specific design of vario- was based on covalent bonds between template mo- us non-covalent interactions such as ionic attractions, lecule and functional monomers. In 1981, Arshady and hydrogen bonding, van der Waals forces, hydrophobic Mosbach introduced a non-covalent approach which is effect and so on [1]. In the development of technology, the most popular method today [6]. It relies on a pre- the structures and operating mechanisms of systems in arrangement of functional monomers with the templa- nature have been inspired. Human innovation by imita- te before polymerization via non-covalent interactions. ting nature is called “biomimetic” or “biomimicry” and In general, molecular imprinting polymers (MIPs) are many of the products used in daily life, industry, military produced via polymerization process of functional mo- etc. have been developed by the biomimetic approach. nomers and crosslinkers in the presence of the temp- Molecular imprinting technology is based on a biomi- late molecule. In MIPs, the selective recognition of the metic strategy allowing synthetic or semi-synthetic target analyte is provided by the tailored-made archi- materials to imitate the molecular recognition seen in tecture of the cavities embedded in the polymer matrix. natural systems [2,3]. Synthetic materials having a ca- Formation of these specific and selective cavities con- pacity of artificial recognition based on molecular imp- sists of three stages (Figure 1): rinting technology go back to Dickey’s research in 1955 Figure 1. General steps of molecular imprinting technology. N. Bereli et al. / Hacettepe J. Biol. & Chem., 2020, 48 (5), 575-601 577 • Self-assembly of selected functional monomers 1. Molecular Imprinting Techniques for Biomimetics around the template molecule 1.1. Separation Techniques • Polymerization of the functional monomers cross- Molecular imprinting technology is widely utilized in se- linking agent in the presence of template molecule paration techniques which can be classified as sample porogens pretreatment and chromatographic separation of bio- • Template removal step resulting in target-specific molecules, pharmaceuticals, environmental pollutants cavities. such as heavy metals and phenolic compounds. For ins- tance, MIPs can be prepared by mimicking antibodies MIPs can recognize the analytes that conform to the in order to purify target antigens. The stationary phase shape and size of imprinted molecular cavities. Mo- prepared using MIPs is more robust and stable, showing lecular imprinting technology enables to synthesize resistance for harsh conditions temperature, pH and target-specific polymers that can recognize biological organic solvents compared with immunoaffinity statio- compounds such as amino acids, proteins, peptides, or nary phases. Moreover, the cost of the stationary phase nucleotides, and also chemicals such as drugs, food ad- with MIPs is lower and its shelf life will be longer due to ditives and pollutants. MIPs can be synthesized in a vari- its high stability. ous shape and size including bulk materials, dendrimers, and micro- and nanoparticles. MIPs can be divided four Recently, molecularly imprinted nanostructures as bi- main approaches with respect to interaction type bet- omimetics of natural antibodies were synthesized [11]. ween functional monomers and template molecule: (i) Cardiac Troponin I is a protein of 209 amino acids and covalent imprinting, (ii) semi-covalent imprinting, (iii) molecular weight of about 23 kDa. Cardiac Troponin non-covalent imprinting and (iv) metal ion coordina- I, a case protein, was chosen for its high diagnostic va- tion mediated imprinting. Because of its outstanding lue in acute coronary syndromes. For this aim, idiotipic features such as easy production, low-cost, reusability, peptide of Troponin I was used as a template molecule mechanical and chemical stability, molecular imprinting and highly crosslinked poly(acrylamide-co-methacrylic technology has been attracted in a wide range of fields acid) nanoparticles (NPs) were prepared via precipita- including separation and purification studies, biosen- tion polymerization. The effect of monomer ratio to sors, catalysts, drug delivery systems and so on [7-10]. Figure 2. General classes of separation application methods using MIPS. 578 N. Bereli et al. / Hacettepe J. Biol. & Chem., 2020, 48 (5), 575-601 template on the formation of the binding sites were Molecularly imprinted cryogel columns were produced investigated. The maximum imprinting efficiency was for selective aflatoxin extraction from food samples [17]. found in the range of 175:1–437:1. Because of their outstanding feature, i.e. mimicking natural antibodies, aflatoxin subtypes B1, B2, G1, and Enantiomeric pharmaceuticals have a diverse effect on G2 imprinted cryogels are named as multiclonal plas- living organisms. Ofloxacin, a new kind fluorinated quino- tic antibodies. The cryogels were characterized by Fo- lone, is a broad-spectrum antibiotic commonly used for urier transform infrared (FTIR) spectroscopy, scanning treating bacterial infections. S-ofloxacin is 8–128 times electron microscopy (SEM), and spectrofluorimetry. Se- stronger in preventing the growth of gram bacteria than lectivity of the imprinted cryogels were studied using R-ofloxacin, and almost two times more active than the ochratoxin A and aflatoxin M1 as competing agents and racemic ofloxacin [12,13]. Molecularly imprinted magne- imprinting efficiency of the imprinted cryogels
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