“The use of biomaterials for industrial applications has increased significantly. Carbon footprints rationalization and food vs. fuel dilemma have been debated and made considerable progress towards a wider acceptance at various levels. Open innovation contributes meaningfully with regards to: softer, milder temperature biochemical processing which includes preconditioning, low stress reactions, “just-as-needed” purifications, zero waste, fallow land exploitation rationalization, usable agri-waste, traceable land use, water consumption minoration vs. agronomical food-related practice, partial detachment from international seasonal trading of agricultural commodities…” [1] .

In this context, our journey across the “rurban” zones is evolving. The sightseeing is a planet “responsible” fairytale that is coming closer to reality; locally produced, synergically codependent energies. Piezo (due for example to the unique crystalline structure and piezoelectric behavior of cellulose as described later in Section 2.2) and solar photovoltaic road paving, quietly growing CO₂ harvesting forests, prairie and golden fields ecofuel providers… are among the multi centennial castles, monuments and mills now wind, solar and hydraulic universal converters.

Along this fairy trail, alternative energies (Figure 1), as well as new energy usage patterns are promoting innovation in the field of energies’ production, transmission, transformation, distribution and local usages.

“The emotional intelligence has become a recognized essential part of a global ‘balance’, in this virtual-reality.” Let’s see what we said some about 20 years ago, on related skills [2] .

“Can we foresee the profile of the next generation of scientists and engineers? The people behind innovation are essential to establish the foundations of the

future successful businesses. In the chemical industry, the chemist, the physicist, the material scientist, the engineers are playing an important role in the creative process which is required to follow the pace of change. New organizational concepts have been proposed in order to schematize the industry adaptation to this ‘new’ global environment. We found that most of them require from the people a balance of skills which we propose to abbreviate with the acronym 4C, where the 4Cs represent: Connaissance, Creativity, Competence, Communication. ‘Pursuing with’, the bubble concept is one way of stimulating innovation. It is possible to combine enterprises or projects A, B, C in a way that the mentors, the promoters, the generators of the enterprise A have a chance to play another role in B or in C…”.

Figure 2 below helps capture more about the above 4C innovative tetralogy.

The number of current innovation styles, from open to close, disruptive, collaboratory®, from reverse to inclusive, nested and frugal, are more or less self-explanatory terminologies and further enlightenment can be found, e.g. in Lapray et al. [3] [4] in reviews on the matter, covering some of them [5] .

More literature on artistic creation and more expressly musical art is dedicated to the innovation traits of musical production, rather say improvisation; Jazz is of an established relevance.

Figure 3 attempts to provide the 4C’s corresponding Jazz terms and concepts therewith developed by the expert Charles Calamel [6] , in the creation, integration, self learning and improvisation model that Jazz culture continues to develop spontaneously.

One may further cite Charkes Calamel proposed acronym “CRAC” [6] , with stands for Competent, Responsible, Autonomous, Creative… definitely a series

of traits that innovation in the bigger data surrounding cannot miss.

Charles Calamel, (http://www.touteduc.fr/fr/archives), says: “Jazz is a model in that it leads the individual towards a self-direction in learning, a construction of oneself. Due to the conditions of play, the respect and transgression of codes and formats, jazz reverses the traditional pedagogic guidance system to set up a model of autonomy: it is not a question of receiving knowledge but rather of ‘Go find it’ ”.

Fred Hersch’s song title “Songs without Words” may further highlight the improvisation nature and emotional intelligence of creativity and innovation.

Emotional intelligence which may become more central to diversity innovative approach, to capture developmental potential, may not fit within the trend of bigger data and artificial intelligence interaction; although the later may be a source of improvisation.

In that domain D. Lapray and S. Rebouillat [3] presented some anticipatory aspects in a review: “‘Bigger Data’ Visualization to Visual Analytics: a path to Innovation. ‘Happening, definitely! Misleading, possibly?’ A review of some examples applicable to IP Discovery.” The authors pointed out that aesthetic may be privileged and can be misleaded. Figure 4 below is a clear demonstration.

In Figure 4, out of [3] , “the same analysis was applied to the title of 1000 patents in the field of natural polymers. The 13 top nodes are displayed using the Kamada-Kawai layout (well known force-directed graphs). The three panels represent the exact same data on which the layout was reinitialized three consecutive times. Note that only the nodes, edges size and color are maintained between these three representations. These are the only relevant information, the rest being purely aesthetical.”

No need to be a professional in the advertisement arena or a malicious developer, of fake impression carried by photography angle shot selections, to realize that the above triangles configurations of Figure 4, with bold solid heavy black sides, although linking the same matters, Composit (es)-Fiber (s)-Materi (als) & (Polym (ers)) may, take different dimension pending on the persons observing these figures, their mindset of the time.

There is indeed an improvising dimension that may arise from bigger data analysis and visualization. Such as the representation on the left side may give a sharp and central dimension of the three first matters of Composit (es)-Fiber (s)-Materi (als)-(Polym (ers)), the central representation may imply a massive bulk dimension of the four, and the representation on the right may elude to a side lateral importance of the three first. Analogically the jazz player may improvise some mimics and positionings that will attract attention on some elements of his production and interactions.

The improvision dimension of innovation is certainly a way to liberate the creator away from core dimensions; those are prevalent and revealed in patent analysis wherein a language rarely changes as long as it is in the core corporate language and know hows. Laterals and boundaries are efficient add-ons in an inventive concept presentation.

In a nutshell, the parallel between innovation and art has been progressively

brought to the attention of the reader from a fairy tale landscape making innovative use of natural resources keeping “monuments in place”. Followed by the foresee, “4C”, dimension of the collaborative skills developed back in 1998 by Rebouillat. Extended to the Jazz science to education breadth and its self-learning integration value; associated with a high degree of intrinsic improvision. Closing the loop with the bigger data and artificial intelligence emotional limitations and potential for misleadingness that may deserve a longer propos in a review to come.

Instinctive and improvisional innovations are to be added on the list of [4] .

Additional references on the above fields with selected technology domains are useful [7] - [13] .

The present paper follows up on three reviews [14] [15] [16] that we published on important researches related to the valorization of biomaterials, one of them [14] reached record downloads of 10,500 and 17,500 views, which supports the interest for scientific expert reviews in the context of bigger data; obviously big data consolidation can still improve to be even more useful to the “trained in the art”.

Smart or functional materials form a group of new and state of art materials now being developed that will have a significant influence on many of present-day technologies. Also called active materials, smart materials have the intrinsic and extrinsic capabilities, first, to respond to stimuli and environmental changes and to activate their functions according to these changes [17] [18] . The stimuli could originate internally or externally. Examples of external stimuli can be temperature, pressure, electric and magnetic fields, chemicals, light, humidity, hydrostatic pressure, nuclear radiation, pH and more. Smart material responds to those stimuli with changes in their internal structure and intrinsic properties such as shape, stiffness, viscosity, energy absorption capacity, damping or optical properties like transparency or opacity.

Most smart materials have reversible properties, reverting back to their original state after the stimulus is removed or changed. The cycle can then be repeated. Smart materials are also tailorable and tunable, which means they can be designed for specific, controlled property changes. To achieve a specific objective for a particular function or application, a new material has to satisfy specific qualifications related to technical and technological properties, economic criteria, raw material and production costs, supply expenses and availability, environmental characteristics and sustainable development criteria, implying reuse and recycling capacities.

If the functions of sensing and actuation are added to this list, the new material is considered a smart material [19] . Since the 1990s, a lot of research efforts have been devoted to the development [20] [21] [22] and industrial application [23] [24] of smart materials. Examples of some well-known smart materials are piezoelectric polymers [25] , piezoelectric ceramics [26] , shape memory alloys [27] , electro-active polymers [28] , covalent adaptive network polymers [22] and electrorheological and magneto rheological fluids [29] .

Many other materials with added functions: have also been developed. They concern 1) sensor materials to detect certain signals, adjust sensitivity according to environmental changes, or restore degraded sensitivity, 2) catalytic materials to detect the progress of a reaction or distinguish the reaction of a product, 3) textile materials to detect a variety of signals from the human body and weather conditions so as to allow for greater comfort.

Smart composite materials: are also manufactured by combining two or more single smart materials in order to utilize synergistically the best properties of their individual constituents. Many of those composites are able to satisfy all of the above specific qualifications. Their advantages and adaptability to the design requirements mentioned above have led to a profusion of new products. There are two essential types of smart composite materials 1) completely tailored man-made composite materials which purpose is to improve or add strength or stiffness, 2) amalgamation of single/composite materials with fibre/reinforced polymers (FRPs) such as the ones used as reinforcement for concrete, steel or other construction materials. If the FRP is combined with fibre optic sensors, the resulting product will be an attractive and particularly cost effective smart composite.

A smart structure is a system that incorporates particular functions of sensing and actuation to perform smart actions in an ingenious way. It is composed of the following components:

・ Data Acquisition (tactile sensing) which collects the required raw data needed for an appropriate sensing and monitoring of the structure.

・ Data Transmission (sensory nerves) to forward the raw data to the local and/or central command and control units.

・ Command and Control Unit (brain) which manages and controls the whole system by analyzing the data, reaching the appropriate conclusion, and determining the actions required.

・ Data Instructions (motor nerves) which transmits the decisions and the associated instructions back to the structure.

・ Action Devices (muscles) which take action by triggering the controlling devices/units.

The Main areas of R&D involved in smart materials are:

・ For sensors and actuators: photo-sensitive materials, fibre optics, conductive polymers, thermally sensitive materials, shape memory materials, intelligent coating materials, chemical responsive materials, micro-capsules, micro- and nano-materials.

・ For signal transmission, processing and control: neural networks and control systems, cognition theory and systems.

・ For integrated processes and products: wearable electronics and photonics, adaptive and responsive structures, bio-mimics, tissue engineering, chemical/drug releasing.

Figure 5 summarizes how does a smart material works.

In the last ten years, the field of smart materials has received much attention as a result of the development of new electro-active polymer (EAP) materials that exhibit a large displacement displacement response which changed the potential capability and paradigms of these materials. The main attractive characteristic of EAP is their operational similarity to biological muscles, particularly their resilience and ability to induce large actuation strains [30] . This characteristic is a valuable attribute that has enabled a myriad of potential applications, and it has evolved to offer functional similarity to biological muscles. EAP materials are able to offer a range of performance and characteristics that may not be reproduced by other technologies. Therefore, it is rather certain that EAP materials have a promising future for applications, such as biologically inspired actuators driving various mechanisms for manipulation and mobility including micro-robots, micro-flying objects, and animatronic devices.

Today, the focus is on specialty products engineered for specific end-uses and on creative ways to market these products and the current generation of smart materials has many new dynamic features that enable them to adapt to the environment and make them the materials of the future, mainly, as this will be further outlined in this paper, in the domain of renewable biomass-materials.

The present paper follows upon three reviews [14] [15] [16] that we published on important researches related to the valorization of polysaccharides with the objectives of reducing the fossil resource dependence and producing therefore environmentally-friendly new materials. Indeed, the great biodiversity of nature (i.e., plants, animals, insects, enzymes, microbes, etc.) coupled with the enormous advances developed in biotechnological processes, makes it today possible, through adequate transformations of bio-sourced products, to elaborate high

value-added sustainable products endowed with physical, chemical and biological properties leading to particularly innovative applications.

This paper reviews recent works developed on those natural resources with the objectives of manufacturing smart materials. The biosourced products which will be considered are polysaccharides, including cellulose, hemicelluloses, chitin, chitosan, alginates, and their by-products (copolymers, blends and composites).

Polysaccharides are the most abundant materials that can be obtained from renewable and sustainable resources. They are biodegradable, carbon neutral with low environmental, health and safety risks and serve as structural material in the cell walls of plants. Some of them (e.g. cellulose and hemicelluloses) are used, for many years, as engineering material in many industrial processes such as pulp and papermaking and manufacture of synthetic textile fibres (e.g. organic and inorganic esters, alkyl, hydroxy alkyl and carboxyl alkyl ethers) which are important components in coatings, optical films, foodstuffs, pharmaceutics, cosmetics, additives in building materials, etc. [14] .

Moreover, owing to polysaccharides properties, functionality, durability and uniformity, their use continue today in other domains (e.g. conversion into biofuels such as ethanol as an alternative fuel source and, more recently, in the design of processes using polysaccharide nanoparticles for the generation of novel polysaccharide-based biomaterials and composites [14] ).

On the other hand, it is noteworthy that chemical modifications of polysaccharides, “tailor-made” towards specific properties can also result in new materials, including smart materials. Indeed, owing to their unique and valuable functional properties, modified polysaccharides can confer smartness through somewhat unique mechanisms such as:

・ reversible, stimuli-responsive self-assembly (gelation),

・ biospecific interactions with enzymes and lectins (carbohydrate-binding proteins)

・ And interactions that confer nanoscale (e.g. fibril-forming) and hierarchical supramolecular assembly.

Nevertheless, today, the fundamental understanding of the molecular level interactions that confer smartness to polysaccharides remains relatively poor and one can predict that new experimental and theoretical tools will emerge to develop the necessary understanding of the structure-property-function relationships that will enable polysaccharide-smartness to be better understood and controlled, giving rise to the development of new and innovative applications. This would allow making polysaccharides materials of choice in the very promising areas of nanotechnology, foods, cosmetics and medicine (e.g. controlled drug release [31] and regenerative medicine [32] [33] ) and so, opening up major commercial markets in the context of green chemistry.

Despite its high hydroxyl groups content, cellulose has limited functionalities and, to our knowledge, there are very few reviews on “smart” materials based on cellulose unless hydrogels which were referred to [39] [40] [41] . Nevertheless, the physical structures of cellulose fibers, (particularly cellulose nanofibers: CNFs) and nanoparticles (nanocelluloses: CNCs), have opened up interesting opportunities to manufacture blends and composites used to make high valued products (Table 1).

CNFs photo-responsive nature can act as adaptive fillers in soft polymer matrices. CNCs properties such as low density, thermal stability, chemical resistance, high mechanical strength, biocompatibility and biodegradability allowed to consider them as functional materials in actuation systems and sensors for detecting pH, organic vapors, ions and humidity [39] [42] .

CNC based smart materials display intelligent behavior in response to environmental stimuli such as light, temperature, electrical input, pH, and magnetic force [43] [44] [45] . Moreover, owing to their high aspect ratio and mechanical properties, CNCs can also serve as renewable reinforcing agents in nanocomposites, as well as a handle for adding stimuli responsiveness [46] .

On the other hand, the properties of cellulose enable cellulose to be applied to the vast fields of smart electroactive polymers and hydrogels which can be fabricated through chemical modifications or physical incorporating/blending processes.

Chemical modifications of cellulose are realized using homogeneous or heterogeneous processes.

Homogeneous processes are mainly carried out by dissolution of cellulose derivatives (e.g. carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and cellulose acetate (CA)) in suitable solvents (e.g. water or common organic solvents).

Heterogeneous processes are usually performed, after swelling in suitable solvents, on cellulose nanocrystals (CNCs), films/membranes, fibers, and cellulose particle suspensions.

In the processes of physical incorporating/blending, cellulose or cellulose derivatives act as matrices, fillers, or coatings/shells [15] .

Recently, cellulose has been discovered as a smart material named cellulose-based electroactive paper (EAPap) [54] [55] [56] [57] . The electroactive behavior of EAPap is due to the unique crystalline structure and piezoelectric behavior of cellulose [58] . Indeed, cellulose II crystal is monoclinic and non-centrosymmetric in nature and thus it exhibits piezoelectric characteristics [54] [59] [60] . This piezoelectricity is able to induce large displacement output, low actuation voltage, and low electrical power consumption in the application of biomimetic sensors/actuators and electromechanical system.

Moreover, nanocellulose-based EAPap portrayed several superior characteristics such as ultra-lightweight, large bending deformation, low actuation voltage and low power consumption. These characteristics are very appealing for delicate biomimetic actuators and sensors, dynamic wings for flying articles, active sound-absorbing materials, adaptable speakers and smart shape control gadgets [56] [61] (Table 2).

In addition, preparation of nano-cellulose-based smart material via chemical modification and physical incorporation or blending in various forms can affect

responsiveness to pH, temperature, light, mechanical forces, electricity, and magnetic field. The presence of porosity and refractive index variation has made EAPap a feature with extraordinary light-scattering effect (used as a transparent paper) for use in integrated transparent sensors and 3D microfluidic application.

However, even if there are already many potential applications for cellulose EAPap, it must be noted that, today, several important challenges remain and should be considered, for example in terms of reliability, material robustness and force improvement.

Gels are three-dimensional natural or synthetic polymer networks that can swell and absorb large amounts of solvents without dissolving, provided that chemical or physical crosslinks exist among the macromolecular chains.

Hydrogels are, mainly, structures formed from biopolymers and/or polyelectrolytes, and contain large amounts of trapped water. They can be divided into chemical gels and physical gels. Chemical gels are formed by covalent bonds while physical gels are formed by molecular self-assembly through ionic or hydrogen bonds [72] . They have wide potential applications in the fields of food, biomaterials, agriculture, water purification, etc. (Table 3).

Responsive hydrogels can undergo a swelling transition in response to environmental stimuli, such as the changes in temperature, light, pH, etc. Because of this unique feature, responsive hydrogels have received an extensive attention in the fields of drug delivery [82] , bioseparation [83] , sensors, and optical transduction of chemical signals [83] [84] . For example, the drug release from responsive hydrogels can be remotely controlled by the local heating of magnetic nanoparticles [85] . The same concept has been transferred to the application in catalytic reaction, which is particularly attractive due to the unique tunable and responsive properties as well as the improvement of reactive properties [82] [83] [84] . Specifically, the swelling and deswelling of the hydrogel with temperature

change can control the loading/unloading of reactants in the hydrogel network, which, in turn, changes the reactivity.

There are plenty of methods for preparing hydrogels. The mixing of anionic and cationic polymers solutions is widely used for preparing reversible hydrogels. The final properties of the 3D network of physical hydrogel should depend on several factors such as the anionic/cationic charge ratio, the pH and the existence, or not, of stirring and the respective speed during the preparation, as well as several other parameters.

After these basic definitions and examples, the following paragraphs aim at highlighting some of the most recent developments in cellulose-based hydrogels materials, including pure cellulose, cellulose composite and cellulose hybrid hydrogels.