Studies in Natural Products Chemistry Volume 45 Edited by Atta-ur-Rahman, FRS International Center for Chemical and Biological Sciences H.E.J. Research Institute of Chemistry University of Karachi Karachi, Pakistan AMSTERDAM • BOSTON • HEIDELBERG • LONDON NEW YORK • OXFORD • PARIS • SAN DIEGO SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK 225 Wyman Street, Waltham, MA 02451, USA Copyright © 2015 Elsevier B.V. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. 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ISBN: 978-0-444-63473-3 ISSN: 1572-5995 For information on all Elsevier publications visit our website at http://store.elsevier.com Contributors Rohaya Ahmad Atta-ur-Rahman Institute for Natural Product Discovery, and Faculty of Applied Sciences, Universiti Teknologi MARA, Selangor, Malaysia Andrzej Bajguz Department of Plant Biochemistry and Toxicology, Institute of Biology, University of Bialystok, Bialystok, Poland Iwona Bąkała Department of Plant Biochemistry and Toxicology, Institute of Biology, University of Bialystok, Bialystok, Poland Leandro Machado de Carvalho Universidade Federal de Santa Maria – UFSM, Campus universitário, Santa Maria, Rio Grande do Sul, Brazil Gerardo Cebrián-Torrejón Department de Química Analítica, Universitat de València, Burjassot (Valencia), Spain; Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo – USP, São Paulo, Brazil Angela Chambery Department of Environmental Biological and Pharmaceutical Sciences and Technologies, Second University of Naples, Caserta, Italy Łukasz Cieśla Department of Inorganic Chemistry, Faculty of Pharmacy, Medical University of Lublin, Chodźki, Lublin, Poland Massimo Curini Department of Pharmaceutical Science, University of Perugia, Perugia, Italy Brigida D’Abrosca Department of Environmental Biological and Pharmaceutical Sciences and Technologies, Second University of Naples, Caserta, Italy Antonio Doménech-Carbó Department de Química Analítica, Universitat de València, Burjassot (Valencia), Spain Mehmet Emin Duru Department of Chemistry, Faculty of Science, Muğla Sıtkı Koçman University, Kötekli, Muğla, Turkey Antonio Fiorentino Department of Environmental Biological and Pharmaceutical Sciences and Technologies, Second University of Naples, Caserta, Italy Jyotirmoy Ghosh Natural Product Chemistry Division, CSIR-North East Institute of Science and Technology, Jorhat, Assam, India Zbigniew Janeczko Chair and Department of Pharmacognosy, Collegium Medicum, Jagiellonian University, Medyczna, Cracow, Poland Takaomi Kobayashi Department of Materials Science and Technology, Nagaoka University of Technology, Nagaoka, Niigata, Japan Lie-Feng Ma College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou, Zhejiang, P. R China xi xii Contributors Elsebai Mahmoud Fahmi Nice Institute of Chemistry, Bioactive Molecules Team, UMR 7272 CNRS, Nice Sophia Antipolis University, Nice, France; Department of Pharmacognosy, Faculty of Pharmacy, Mansoura University, Mansoura, Egypt M. Carla Marcotullio Department of Pharmaceutical Science, University of Perugia, Perugia, Italy Mariele Martini Universidade Federal de Santa Maria – UFSM, Campus universi- tário, Santa Maria, Rio Grande do Sul, Brazil Federica Messina Department of Pharmaceutical Science, University of Perugia, Perugia, Italy Mehiri Mohamed Nice Institute of Chemistry, Bioactive Molecules Team, UMR 7272 CNRS, Nice Sophia Antipolis University, Nice, France Akhtar Muhammad Department of Chemistry, Faculty of Science, Muğla Sıtkı Koçman University, Kötekli, Muğla, Turkey Legrave Nathalie Nice Institute of Chemistry, Bioactive Molecules Team, UMR 7272 CNRS, Nice Sophia Antipolis University, Nice, France Mamona Nazir Institute of Pharmaceutical Biology, Nussallee, Bonn, Germany Mehmet Öztürk Department of Chemistry, Faculty of Science, Muğla Sıtkı Koçman University, Kötekli, Muğla, Turkey Amade Philippe Nice Institute of Chemistry, Bioactive Molecules Team, UMR 7272 CNRS, Nice Sophia Antipolis University, Nice, France Ornelio Rosati Department of Pharmaceutical Science, University of Perugia, Perugia, Italy Muhammahd Saleem Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur, Pakistan Fatimah Salim Atta-ur-Rahman Institute for Natural Product Discovery, Universiti Teknologi MARA, Selangor, Malaysia Monica Scognamiglio Department of Environmental Biological and Pharmaceutical Sciences and Technologies, Second University of Naples, Caserta, Italy Valeria Severino Department of Environmental Biological and Pharmaceutical Sciences and Technologies, Second University of Naples, Caserta, Italy Wei-Guang Shan College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou, Zhejiang, P. R China Parames C. Sil Division of Molecular Medicine, Bose Institute, Kolkata, India Marta Talarek Department of Plant Biochemistry and Toxicology, Institute of Biology, University of Bialystok, Bialystok, Poland Gülsen Tel-Çayan Department of Chemistry, Faculty of Science, Muğla Sıtkı Koçman University, Kötekli, Muğla, Turkey Pınar Terzioğlu Department of Chemistry, Faculty of Science, Muğla Sıtkı Koçman University, Kötekli, Muğla, Turkey Drochss P. Valencia Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo – USP, São Paulo, Brazil Contributors xiii You-Min Ying College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou, Zhejiang, P. R China Daniel Załuski Chair and Department of Pharmacognosy, Collegium Medicum, Jagiellonian University, Medyczna, Cracow, and Faculty of Health Sciences, Almamer University, Wolska, Warsaw, Poland Zha-Jun Zhan College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou, Zhejiang, P. R China Preface The present book represents the 45th volume of this long-standing series that has become the most comprehensive encyclopedic treatise in the field of natural products. In Chapter 1, Kobayashi reviews the use of cellulose from bagasse wastes to fabricate hydrogel films with flexible and bioactive properties that can be used in tissue engineering. Different applications of cellulose fiber nanostructures of the hydrogel films are discussed. Marcotullio et al. discuss the important bio- logical activities of Cannabis and the efforts aimed to the discovery of natural and nonnatural selective cannabinoids in Chapter 2. In the next chapter, the new applications of electrochemistry that provide information about the phar- macological activity of natural products are reviewed by Doménech-Carbó et al. These include the electrochemical testing of specific pharmacological activity by electrochemical screening, in situ evaluation of drug–substrate interactions, and electrochemical mimicry of selected biological redox processes to observe correlations between molecular structure, redox properties, and pharmacologi- cal activity. In Chapter 4, recent advances in structural elucidation of saponins by NMR and MS are discussed by Scognamiglio et al. Phytoecdysteroids belong to a large family of ecdysteroids that comprises more than 250 representatives. The pharmacological effects of these com- pounds in vertebrates and humans are discussed by Bajguz et al. in Chapter 5. Drimane-related merosesquiterpenoids are complex natural products that occur frequently in lower organisms and rarely in higher plants. The classification, biosynthesis, and bioactivity of these compounds are discussed by Zhan et al. in Chapter 6. In Chapter 7, the recent advances in researches on the structure– activity relationships of secondary plant metabolites with antimicrobial, free radical-scavenging activities and inhibitory properties against selected enzymes are presented by Załuski et al. Marine polyacetylenic compounds exhibit a variety of biological activities including antimicrobial, antifouling, cytotoxic, antiviral, and anti-inflammatory activities. They therefore offer interesting molecular models for the development of new pharmaceuticals. This area is reviewed in the next chapter by Nathalie et al. In Chapter 9, Saleem has presented the isolation, characterization, and bio- logical studies of more than 500 natural products from marine-derived fungi, published during 2006–2012. In the next chapter, Ozturk et al. review the polysaccharides, terpenoids, steroids, phenolics, and alkaloids isolated from xv xvi Preface mushroom species along with their biological activities. In Chapter 11, Sil et al. assess the potential of natural products in the field of organ pathophysiology. In the final chapter, Ahmad and Salim present the chemical, biological, and phar- macological properties of oxindole alkaloids from Uncaria species along with their potential for drug development. I am confident that the readers will find the present volume of great interest. I would like to thank Ms Taqdees Malik and Ms Humaira Hashmi for their assistance in the preparation of this volume. I am also grateful to Mr Mahmood Alam for editorial assistance. Atta-ur-Rahman, FRS International Center for Chemical and Biological Sciences H.E.J. Research Institute of Chemistry University of Karachi, Karachi, Pakistan Chapter 1 Fabrication of Cellulose Hydrogels and Characterization of Their Biocompatible Films Takaomi Kobayashi Department of Materials Science and Technology, Nagaoka University of Technology, Nagaoka, Niigata, Japan E-mail: [email protected] Chapter Outline Introduction 1 Cellulose Hydrogel Bioactivity 8 Fabrication of Cellulose Films and Cellulose Scaffold Biocompatibility Their Properties 3 and Cytotoxicity 8 Phase Inversion Processes for Concluding Remarks 12 Fabricating Hydrogel Films from List of Abbreviations 13 Plant Cellulose 4 Acknowledgments 13 Characterization of References 13 Hydrogel Films 5 INTRODUCTION Attention has been increasingly devoted to bio-based environmentally friendly materials because of increasing environmental concerns related to sustainability, in addition to their interesting bioactive properties. Since the dawn of civilization, bio-derived and natural materials have been regarded as a fundamental part of human life. However, because of natural resource exploitation and cost issues, synthetic materials are replacing bio-derived materials in many industrial prod- ucts. Accordingly, a persistent and unsatisfied need exists to develop novel bio- materials that are readily producible from renewable resources at reduced cost and for a broad array of useful applications. Therefore, regeneration or direct utiliza- tion of waste plant sources can provide a new generation of recyclable engineered materials. Understanding the structures and functional characteristics of these novel biomass materials is expected to expedite the design and fabrication of eco- friendly or recyclable advanced materials, especially for cellulose (Fig. 1) [1–5]. Studies in Natural Products Chemistry, Vol. 45. http://dx.doi.org/10.1016/B978-0-444-63473-3.00001-0 Copyright © 2015 Elsevier B.V. All rights reserved. 1 2 Studies in Natural Products Chemistry FIGURE 1 Chemical structure of cellulose. FIGURE 2 Cellulose hydrogel films showing flexibility and strength. As described herein, a natural plant polymer originating from agave bagasse waste is used for regeneration to cellulose. Bagasse, a waste product mainly deriving from sugarcane production, and its residues are known to consist prin- cipally of cellulose, hemicelluloses, and lignin, which are useful resources for use in producing biopolymers. For use in producing cellulose having abun- dant hydroxyl groups, pure hydrogels of the biopolymer are fascinating. For instance, Agave tequilana Weber azul is an economically important plant culti- vated in central Mexico for the production of tequila [6,7]. The brown bagasse fibers can be treated to transform them to white cellulose fibers using processes [8,9] including (1) lignin removal and (2) bleaching of the cellulose fibers. This material is then converted using a new preparation technique for pure cellulose hydrogel films [8,10]. Phase inversion processing of cellulose with N,N-dimeth- ylacetamide (DMAc)/lithium chloride (LiCl) solution to solidified hydrogel film enables the fabrication of transparent and flexible cellulose films (Fig. 2), which are obtainable without additional chemical cross-linking. As reported from our earlier results [8], experimental evidence shows that the resultant hydrogel film has unique properties. These films possess good mechanics and viscoelasticity in their water-swollen condition. The hydrogel behaviors in cellulose structure and characteristics are described using several analytical methods to assess the nanostructure. In addition, with the fabrica- tion of the hydrogel films, effects of the nanostructure on their biocompatibility and cytotoxicity are described as bioactive characteristics of cellulose hydro- gel films. Therefore, such a cellulose scaffold for tissue regeneration can be expected to become an excellent platform technology supporting medical appli- cations. The unique properties of swelling hydrogels are reviewed in this article for fabrication. These properties include evidence of flexibility at swelling con- ditions and cell cultivation on the hydrogel scaffold. Fabrication of Cellulose Hydrogels Chapter | 1 3 FABRICATION OF CELLULOSE FILMS AND THEIR PROPERTIES Cellulose, the major biomacromolecule in plant cell walls, has a long history as a natural resource [1], providing numerous benefits related to its biocompatibil- ity and biodegradability [2]. Cell walls of wood play an important role in main- taining wood’s tensile strength and flexibility [3–5]. These properties enable its use in our daily life, but they also show potential for numerous applications as bio-based materials such as fibers, films, food casings, and membranes. In fact, biomedical uses have garnered great attention recently because of increased interest in tissue-engineered products for both wound care and damaged organ regeneration [11,12]. Nonwoven ribbons of microbial cellulose microfibrils closely resemble the structure of native extracellular matrices (ECM), suggest- ing that it can function as a scaffold for the production of numerous tissue- engineered constructs. In contrast, difficulty in fabricating cellulose to create films and other prod- ucts is known. Generally, film sheet processing can be conducted using such a cellulose solution. However, cellulose is neither meltable nor soluble in water or common organic solvents because of its partially crystalline structure and strong hydrogen bonds. For this reason, over a long time, the processibility and utilization of cellulose have remained limited by the lack of a suitable solvent for cellulose regeneration processes. Some studies for representative solvent systems of cellulose have shown the following. The preparation of cellulose- based biodegradable films was examined [13–15]. In recent years, considerable attention has been directed to biodegradable cellulose-based films [16] when several cellulose solvent systems were available for dissolving cellulose, such as DMAc/LiCl systems [17], N-methylmorpholine-N-oxide [18], NaOH–water with or without additives [19], and ionic liquids [16,19–23]. Some studies have been conducted to prepare cellulose-based biodegradable films using compos- ites [13,23,24] blended with plasticizer for starch-poly(vinyl alcohol) blend films [14] as used with mixtures of cellulose film, hydrogel, and composite plastics. Solvent soluble celluloses such as sorbitol glycerol [25], and carboxy- methyl cellulose [26] are alternatives for use in producing cellulose films. A typical experimental procedure for cellulose film preparation is followed by evacuation [16] and solvent exchange processes [25]. Nevertheless, pure cel- lulosic films present difficulties related to fabrication with problems related to the improvement of brittleness characteristics, poor mechanical behavior, and water sensitivity. More recently, nanosized cellulose fibers have been used for the development of transparent cellulose films [27–29]. However, key diffi- culties have restricted their uses in widely various applications of cellulose, especially for hydrogel films containing hydrated water. Bioactivity appears in a water medium and in hydrated conditions of macromolecular environments. Therefore, such gelatinic materials are interesting and attractive for bioactive applications. Some hydrogels are prepared mainly by cross-linking reactions of water-sol- uble polymers, as cited in references, especially for biomaterials and bioactive