What We Do Not Know

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Technology in Society 29 (2007) 43–61 www.elsevier.com/locate/techsoc

Nanotechnologies: What we do not know Vuk Uskokovic´ Jozˇef Stefan Institute, Advanced Materials Department, Jamova 39, 1000 Ljubljana, Slovenia

Abstract This paper considers the impossibilities, uncertainties and undefined relationships that may be involved in extending scientific and humanistic interest towards the development of nanosciences and nanotechnologies. The author proposes a closed loop that moves from material properties, to synthesis procedures, to applied functioning of nanoproducts and their place within ecosystems and societies, to the design of novel features of nanomaterials. Unpredictabilities that may occur in the transition from micro to nano within material structures are described. The paper then discusses trial-and-error approaches and self-organization effects within every nanodesign procedure, and considers the impossibility of forming perfect nanoproducts. Uncertainties arising from environmental effects, and the extensive future use of nanoproducts within bio/technological interfaces pave way for the study of GM case and discussion of sustainability and zero-waste potential. r 2006 Elsevier Ltd. All rights reserved. Keywords: Nano; Nanoscience; Nanotechnology; Genetically modified foods; Sustainability; Zero waste; Trial-anderror approach; Bioengineering; Ecology

1. Introduction This article identifies and discusses many of the functions of science today that seek to produce new materials and technologies often referred to in conjunction with the word ‘‘nano.’’ I believe that keeping abreast with horizons of human knowledge enables modern science to identify further discoveries as well as to develop advanced cultures and even more complex bio-technological interfaces. There are four sections in this paper. Section 2 discusses dramatic changes in material properties that occur with the reduction of grain sizes to nanoscale proportions. Section 3 Tel.: +38614773900; fax: +38612561222.

E-mail address: [email protected]. 0160-791X/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.techsoc.2006.10.005

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considers trial-and-error approaches that can be used to design novel nanostructures, as well as the problem of constructing nanosized products by imposing ‘‘blueprints’’ on self-organizing natural patterns. The unpredictable ecological effects upon environmental introduction of nanomaterials and nanotechnologies are discussed in Section 4, and the paper concludes with consideration of the potential consequences of predefining scientific research at the cost of further developments at fundamental levels of scientific knowledge. In order to interrelate the physical and chemical fields of nanomaterials science with the mainly engineering-oriented field of nanotechnology, relations between preparation processes, structural properties, and functions need to be understood [1]. The goal of today’s nanomaterial scientists is controlling morphology (nanoclusters, nanowires, nanotubes, etc.), structure, composition, and size—the features that define the physical properties of the resulting materials [2]. As a paradigm within materials science and engineering, the linear dependence between inherent properties of materials, procedures of synthesis, and potential functions within techno-appliances is depicted [3]. The growing interest in nanostructured materials is the natural consequence of advances and refinements of knowledge about the creative manipulation of materials. And the more precisely nanomaterial properties are magnified, the more unusual and unexpected features emerge. Unique research fields devoted to endeavours characterized by the prefix ‘‘nano’’—from physical modelling, to chemistry, to discourses on the ethical and eco-prospects of industrial applications—have gradually developed. However, while the scientists’ ability to make artificial changes in the features of nature has increased over time, enabling them to routinely produce extraordinarily complex nanostructures, it should be remembered that nanoparticles have been present since the beginning of planetary life and the earliest appearance of mankind’s ability to produce arts, tools, and machinery [4,5]. Today’s keen interest in anything nano in the scientific and popular media has undoubtedly been spurred by large investment funds with a vested interest in the creation of ever-finer technological products. The term ‘‘nanotechnology’’ was first introduced by a Japanese engineer, Norio Taniguchi. The term originally implied [6] a new technology that went beyond controlling materials and engineering on the micrometer scale, which had dominated the twentieth century. However, today’s meaning of the word relates more closely to the visionary formulation of Eric Drexler [7], and corresponds to the atom-by-atom manipulative, hardtech processing methodology. However, due to many misconceptions, the latter approach to nanodesign is today generally referred to as ‘‘molecular assembly.’’

2. When macro and micro become nano Nanoscience is here defined as the study of phenomena and the manipulation of physical systems that produce significant information (i.e., ‘‘readable’’ differences [8]) on a spatial scale known as ‘‘nano’’ (109 m ¼ 1 nm), with critical boundaries that do not exceed 100 nm in length at least in one direction. Therefore, nanotechnologies focus on the design, characterization, production, and application of nanoscale systems and components. The boundaries between the physical regions of macroscopic, microscopic, and nanoscopic are not sharp and they depend on the effects being considered [9]. However,

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reducing the grain size of a material below certain limit results in the appearance of either new or changed properties of the material due to:

  

inherent crystalline grains approaching the size of the characteristic physical lengths of the relevant properties; an increase in the proportion of interface defects and their impact on dependent properties; and the appearance of new structural properties that characterize the grain boundaries of the material [10].

For example, a material comprised of spherical crystalline grains 3 nm in diameter finds approximately half of its atoms positioned at grain surfaces, which implies more pronounced reactivity of the system. However, a decrease in grain size, equivalent to an increase in specific surface area of the system, indicates not only increased reactivity but also that physical properties are no longer dominated by the physics of the bulk matter. Since specific disciplines within materials science are normally divided based on the properties of bulk materials, an understanding of the transition from macro to nano offers the opportunity to bridge imposed gaps and create a new multi-disciplinary field of nanoscience [1,9]. Physical properties such as electrical conductivity, microhardness, coercivity, and permitivity decrease in proportion to the average particle size of a material. In case of coercivity versus grain size dependence, however, two effects overlap: one valid for bulk materials and the other appearing when grain sizes approach the sizes of magnetic domains. In the former case, coercivity is inversely proportional to the grain size; in the latter case, the H c ¼ f ðD6 Þ function coincides with experimental dependencies resulting in the appearance of maximum at the point of coherence. Further, since mechanical failure of a material frequently takes place through crack migration processes along grain interfaces, the fact that materials with nanosized grains (down to 10 nm) are stronger compared with their bulk counterparts implies significant modifications of strength and toughness mechanisms as a result of the transition from bulk to nanoscale [11]. Metals that become malleable when microstructurally arranged may prove to have unacceptable levels of creep when their grains are reduced to nanolevel. In contrast, the formability of ceramics is known to improve with the reduction of grain size towards nanoscale. As a result, simple linear extrapolations down to nanolevel, using rules that are valid within micro domains, do not work well in all circumstances. By decreasing physical body sizes down to certain limits, the cohesive influences of gravitational forces give place to Morse function-shaped electromagnetic forces and the quantum effects that arise from electronic properties [9]. When the lower size limit of nanomaterial grains approaches that of regular clusters, quantum effects overcome surface effects and become the dominant factor in defining measured properties. Thus, confinement effects modify electron energy levels, similar to a particle in a box, whereby Coulomb blockade effect arises as a consequence of the discrete nature of electric charges. Ultra-small capacitors at fine grain boundaries might be charged with even single electrons, which strongly influence the subsequent transport of charges through the material [11]. Giant and colossal magneto-resistance effects present additional behaviours typical of systems comprising nanosized critical boundaries [12]. Owing to the complex interplay between surface and quantum effects, each nanostructure can display an array of

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unique potential properties with even the slightest modifications, so specific discussions are needed for each nanosystem. It has been observed that insoluble substances become soluble, or that insulating compounds become conductive when their constitutive particles are reduced to nanosize. For example, gold is an inert and unreactive material in bulk atomic symmetries, but it becomes a highly efficient catalyst as the transition to nanoscale is introduced; silver nanoparticles exhibit bioactive properties that are not found in larger particles [13]. Soft, malleable carbon in the form of graphite becomes stronger than steel, and aluminium can spontaneously combust or even be used in rocket fuel following its transition to nanoscale [14]. Although experiments have led to enormous amounts of data on the transitions from micro to nano, there is still no theoretical scheme by which it would be possible to predict how materials in general might behave when reduced to nanoranges. The difficulty of communication between macroscopic and nanoscopic entities is the central issue in the development of nanotechnologies. Increased sensitivity to environmental effects, as dimensions are diminished towards nanoscale, represents a major challenge. For instance, gaseous particles that are constantly being adsorbed and desorbed from a device’s surface create weight fluctuations that might prove to be a significant constraint in the development of everyday nanoappliances [15]. Also, ubiquitous, random thermal fluctuations impose a ‘‘noise floor’’ below which it is impossible to discern signals from background noise. Minimum operating power, normally 103–106 less than signal levels used for optimal excitement of nanodevices, is therefore set as a fundamental threshold for the operation of nanomolecular machines. According to the laws of quantum mechanics, every form of measurement and communication necessarily perturbs the measured and communicated system. Therefore, designing and performing feedbackpermeated macro-to-nano communications with quantum effects that become significant in nano domain present additional challenges. 3. Approaches to nano design and technology 3.1. Bottom-up and top-down approaches Nanotechnologies are generally considered to be technologies for the ‘‘bottom-up’’ creation of materials and devices, in contrast to traditional ‘‘top-down’’ industrial technologies that cast, saw, and machine chunks of raw materials to produce precisely formed products, small or large, ranging from integrated circuits to jumbo jets. According to the definition of nanotechnology given earlier, any technology that manipulates matter on a nanoscale, including ‘‘top-down’’ techniques, can be denoted as nanotechnological. As ‘‘top-down’’ and ‘‘bottom-up’’ nanoscale designs have reached the point where the best achievable feature size for each set of techniques is approximately the same [16], it is natural to expect that the encounters of these two design systems at nanoscale will result in nanoproductivity that will mark a new era. 3.2. Hard-tech approach and soft-tech approaches In the overall ‘‘bottom-up’’ R&D trajectory that leads to future designs and applications of nanotechnologies, two general pathways can be defined. The first is a hardtech approach [17], which pertains to the use of massive and complex apparati to induce

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atom-by-atom or molecule-by-molecule manipulations, and organize relatively simple building blocks into applicable nanostructural outcomes. The second is the soft-tech approach, which includes the design of complex building blocks via self-assembly by performing manipulations on a macroscopic scale [18]. This approach uses relatively inexpensive and commonly accessible equipment that might—contrary to the hard-tech approach—naturally induce decentralization of power and sustainable proliferation of practical knowledge. Basic research, which lies at the root of every successful development and transfer of advanced technologies in a global society [19], prospers from the use of the latter perspective. The hard-tech approach to the design of nanoproducts typically ignores natural limits and pathways, and imposes anthropocentric purposes on natural substrates. However, the soft-tech approach also lacks the ability to consciously organize synthesized building blocks into processed functional appliances. Nevertheless, optimism continues to flourish regarding the possibilities of the molecular machining approach to nanodesign [20] and the potential to self-organize relatively large and complex structures into hierarchically structured outcomes [21]. While the ideal of ‘‘everything is possible’’ dominates the hard-tech, manipulative approach to the birth of atomically assembling nanotechnologies, a more modest attitude is typical of the self-organizing methodology for designing nanosystems. As Richard Smalley, Nobel Laureate in chemistry and a proponent of soft-tech, puts it: Much like you can’t make a boy and a girl fall in love with each other simply by pushing them together, you cannot make precise chemistry occur as desired between two molecular objects with simple mechanical motion along a few degrees of freedom in the assembler-fixed frame of reference. Chemistry, like love, is more subtle than that. You need to guide the reactants down a particular reaction coordinate, and this coordinate treads through a many-dimensional hyperspace. [22] However, the proponents of a more manipulative, mechano-synthetical approach to the formation of functional nanostructures do not insist that everything is possible. They maintain: The principles of MNT [molecular nanotechnology] involve no new basic science, only new applications. Its development, like the Moon-landing program or any innovative engineering project, will require considerable trial and error learning— that is, many routine, incremental scientific discoveries. Its development will require hard work, but not scientific breakthroughs [20]. This leaves the impression that the limitations of fundamental physico-chemical laws will, through trial-and-error, ascertain what is possible to achieve and what is not possible [20]. Contemporary scientific aspirations to construct nanosized assemblers that can synthesize practically everything in an atom-by-atom fashion are, to a large extent, analogous to the idea of Laplace’s demon, which marked the era of enlightenment. Similarities can be perceived between the former idea of the possibility of mechanosynthesizing everything and the latter idea of the possibility of constructing a computer which, preloaded with the complete set of initial boundary conditions of all the particles of the world and deterministic equations that define their movements and interactions, would be able to calculate and predict any future event throughout space and time.

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However, two features of the man/nature relationship prevent these aspirations from achieving reality: size and complexity. Measuring all the initial parameters of any slightly complex natural system, and calculating all the necessary sets of equations, would require enormous amount of time. Likewise, assembling nanoproducts atom-by-atom would require impractical amount of time. As crude comparisons, a single teaspoon of water (similar in size to a device that could establish communication between a human user and nanosized information) has approximately the same number of water molecules as there are teaspoons of water in all of the Earth’s oceans [23]; or the ratio of one nanometer to the human head is approximately equal to the ratio of the human head to the planet Earth [24]. Future states of natural systems, where every systemic component changes with every other over the course of time, are impossible to predict due to non-linear interactions that govern the relations between inherent systemic variables. Similarly, the complexity of the supra-molecular, hierarchical organization of any nanodevice significantly limits the set of possibly attainable nanoarchitectures. The effects of thermal fluctuations and probabilistic quantum effects at the nanolevel (including hydrogen bonding for some chemistries [25]), as well as the complex environment of chemical reactions that tend to be induced by nanobots [26], may naturally limit the potential set of achievable nanostructures as well as the perfect reproducibility of nanoscale construction. It has been argued that in order for a chemical reaction to occur not only do directly interacting entities need to bump into each other, but also the overall spatial context of the reaction to be initiated must be precisely set in order to obtain the desired outcome [26]. If a scientist hoped to solve this problem by introducing more than one manipulating tip for each entity (or relatively small cluster) near the reaction site, then he/she might realise that there is not much ‘‘room at the bottom’’ as Richard Feynman argues [17]. Achieving balance between vision of absolutely desirable order and natural randomness results in harmony between order and chaos—typical for every biological organization in nature. The larger question is whether future nanodesign can transcend this compromise, which today seems like an inescapable natural necessity. The paradigm of objective realism, as seen through the philosophical interpretations of quantum theory [27,28] and biologically founded constructivist philosophies [29–31] or complexity science [32,33], is a convenient system for organizing knowledge but not a foundation for a comprehensive worldview. All the results of human perception might be seen as interplay between the domains of subjectively interpretative and objectively representative qualities. Inseparable ontological features of the natural world, and interpretative, epistemological spheres of human experience together produce all the perceptive outcomes that stand at the end of every measurement process and at the beginning of each scientific conceptualization. The relationship between nature and man can thus be viewed as preeminent in everything, and approaches to materials and nanotechnological design are no exception. Through the self-organizing approach to nanoengineering design, the doors to stewardship of natural paths open. Contrary to the shallow approach (instigated by proponents of the hard-tech, manipulative, socially and ecologically decontextualized design) according to which an epithet of ‘‘natural’’ is deserved for all endeavours that do not violate fundamental physical laws of nature, a more profound outlook towards nanodesign is created. According to that outlook, only with innovations that preserve the natural diversity of relationships in the living domain can truly long-term creative endeavours be sustained. The design of materials with respecting spontaneous, self-organizing pathways in nature will lead us to nanotechnologies that truly go hand-in-hand with nature.

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With the rise of inventions that accommodated nanostructured materials, most applications were—due to high surface areas of nanoparticles—based on their catalytic activities [34]. However, with the advent of precise nanotectonical manipulations (either using self-assembling systems or ‘‘top-down’’ control), nanomaterials started to find their way into new areas such as electronics, information technology (IT), biotechnology, and medicine [35]. Many ideas focused on how to revolutionize virtually every modern industry by introducing innovative nanosensitive appliances. Coupling self-organizing production of uniform nanosized particles with methods for assembling such multi-atomic units into functional suprastructures offers an elegant way to obtain ultra-fine devices. However, there is still some question as to whether an enormously complex environment similar to cellular interiors would be necessary to achieve that aim. The spontaneous assembly of dispersed atoms on a specific substrate into clusters with precisely defined aggregation numbers and geometries [36] could be a useful starting point. 3.3. Trial-and-error approach It is exceedingly difficult to predict the outcomes of experimental settings that aim to produce new nanostructures and morphologies; indeed, the best results in today’s practical nanoscience come from trial-and-error approaches. There is considerable evidence that slight changes in the condition in experiments of nanoparticle synthesis will produce significant differences in the end results [37]. For instance, replacing manganese ions with nickel ions in an experiment of reverse micellar precipitation synthesis of mixed zinc-ferrite resulted in the production of spherical particles in the former case [38] and acicular particles in the latter [39,40]. When the synthesis of copper nanocrystals was performed in the presence of NaF, NaCl, NaBr, or NaNO3, small cubes, long rods, cubes, and a variety of shapes resulted, respectively [34]. The choice of precipitation agent within in situ preparation of nanoparticles in solution can often result in distinctive morphologies [41,42]. When bromide ions of cetyltrimethylammoniumbromide (CTAB) surfactant in a particular wet synthesis of barium fluoride nanoparticles were replaced by chloride ions (CTAC), the product’s identity was no longer the same, whereas the replacement of 2-octanol by octanol significantly modified the crystallinity of the obtained powder [43]. It has been found that even stirring an aging solution where synthesis reactions take place can have a decisive influence on some particle properties. Thus, using a magnetically coupled stir bar during the powder’s aging time influenced crystal quality, and, in some cases, resulted in a different crystal structure as compared with non-magnetically agitated solutions [44]. In case of the synthesis of organic nanoparticles in reverse micelles, the use of a magnetic stirrer led to the formation of larger nanoparticles compared with particles obtained using ultrasound bath as a mixer, even though no changes in particle size were detected with varying solvent types, microemulsion composition, reactant concentrations, and even geometry and volume of the vessel [45]. Changes in size of volume in which the reactions of nanoparticles synthesis take place (as occurs when the transition from small-scale research units to larger industrial vessels is performed) can result in dramatic variations in some essential properties of synthesized materials [46]. Also, when the same chemical procedure of nanoparticles preparation was performed in closed and open otherwise identical vessels, perfectly uniform spherical particles were produced in the former case but elongated particles of similar narrow size distribution were produced in the latter [46]. Complex modern synthesis pathways (as opposite to relatively simple traditional, solid-state routes) offer unlimited potential

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for each desired chemical compositions. Attractive morphological, microstructural, and hierarchical structural arrangements can be obtained by unexpected and unpredictable starting and limiting conditions during synthesis experiments. In each creative research design, special attention is given to the boundary that separates and links the domains of what is known and possible on one side, and unknowable and impossible to know or obtain on the other. However, discerning unknowable and unattainable from generally impossible to achieve is never easy. Some limits, such as superparamagnetic limits recently overcome by preparing ultra-small but highly crystalline and supra-organized Fe–Pt particles [47], are there to be surpassed. Other limits, like Heisenberg’s uncertainty principle or the laws of thermodynamics, are impossible to transcend. Meta-uncertainties, i.e., uncertainties about uncertainties, present a necessary first step in creative extensions of ‘‘possible–impossible’’, ‘‘known–unknown’’, ‘‘predictable–random’’ boundaries of human knowledge. They are reflected in ever more diverse and mutually developing risks and opportunities, dangers and benefits. New technologies never perfectly solve certain problems they aim to fix, but they do expand the potential options for risks and benefits, keeping them in creative balance, and thus fostering an unending search for innovation and advancement through problem solving. 4. Ecological advantages and risks Although most new technologies aim to solve certain problems, they also carry risks related to their unpredictable effects on the sensitive systemic variables of the environment [48]. As a rule, the more prosperous a technology appears, the more unpredictable consequences and potential dangers it may entail. Therefore, both sides of a new technology—that is, its beneficial development and the possible negative consequences— should be investigated in parallel. Of the US$710 million spent in 2002 by the US government on nanotechnology research, only $500,000 was spent on environmental impact assessments, despite the fact that new materials were a major part of the product pipeline [49]. Many of the favourable ecological features derived from nanotechnological production come hand-in-hand with fears arising out of the uncertainty or dangers of their environmental effects and the possibility of losing control of increasingly destructive functions of nanoproducts. The potential advantages of nanotechnologies include:

  

Opportunities to produce devices that could select and reorganize atoms and molecules of the biosphere with the aim of remedying unbalanced environmental relationships. The possibility of preparing technological products in a ‘‘bottom-up’’ style without producing wasteful and dangerous by-products, as typically occurs with most of today’s current manufacturing processes. The ability to produce more functionally efficient materials and devices with higher strength-to-weight ratios. These could eventually eliminate the need for massive infrastructural power generation systems, stimulate the introduction of renewable, more efficient energy sources, and lead to a reduction of human ecological footprints [50]. Several disadvantageous effects of nanotechnologies also exist.



It is possible that self-replicating nanobots could (in an extreme case) either aggressively [51] or through slowly rising supremacy [52] wipe out the whole biosphere.

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A more realistic scenario of unsustainable applications of nanoproducts could further destabilize the already endangered diversity of the biosphere. They could further extend the existing gap between rich and poor.

Because the development of nanotechnologies is only in its infant stages, predictions of both opportunities and dangers are profuse. Predictions typically fail to match reality, as occurred in predicting the influence of diverse micro-, nano- or liquid-composed chemical substances on the environment. According to the well-known cautionary principle, which states that ‘‘the lack of certainty, given the current scientific and technological knowledge shall not delay effective and proportionate actions to prevent hazards’’ [53], the inability to grasp the whole spectrum of the effects that certain technologies will pose to the environment should not retard efforts to research the possible harmful effects of nanotechnologies before they are introduced to the biological world. Unlike the case of asbestos chemicals (when the span between knowledge of its harmful effects and the introduction of internationally accepted standards of use lasted approximately a century), all indicators of adverse side effects of nanosystems should be carefully considered, even if this process slows down the pace of technological innovation. As technology develops and society evolves, regulatory approaches to environmental, legislative, cultural, and ethical issues must keep pace. Neither an immediate moratorium [14,55] on the release of new nanoparticles nor clinging to an old set of existing regulations conveys the right attitude. However, a creative balance between innovation and regulatory precaution can be achieved. While gaps between science and ethics may occur, they can be bridged through the promotion of multi-disciplinary decision-making processes that include humanistic and ethical guidance of nanodesign [56]. Nanosized particles are more biologically active compared with micron-sized particles of the same chemical composition owing to their greater surface area. Nanoparticles can be used in modern biomedicine treatments in a variety of useful ways: MRI contrast enhancement; hyperthermia treatment [59,60]; drug delivery and targeting [61–63]; magnetic separation, protein detection and purification [64]; magnetic field-assisted radionuclide therapy [65]; magneto-relaxometrical diagnostics and eye surgery [65]; the detection of intracellular molecular interactions [66], with the possibility of developing gene and/or cellular metabolic therapy [67]. Concerns about the possible adverse health effects of nanoparticles include the relative persistence (i.e., several months) of nanoparticles in lung tissue; their potential to pass the blood–brain barrier, to reach brain tissues [57] and induce damage [11]; and their absorption through the skin into the bloodstream [58] via uptake into lymphatic channels. Potential for both inflammatory and pro-oxidant activity on one side, and antioxidant activity on the other has been ascribed to nanosized particles. Although nanoparticles are ubiquitous in ambient and indoor air, in fact they have been present in the environment since the earliest stages of evolution [68]. In a set of toxicological experiments, polytetrafluoroethylene (PTFE) particles with sizes of 20 nm proved lethal upon inhaling, whereas 130 nm sized PTFE particles did not produce any ill effects in the breathing air [48]. These results indicate not just the increased harmfulness of smaller particles but also the fact that a slight change in size becomes significant when evaluating potential toxicity relative to living organisms. Another study concluded that in low concentrations of inhaled nanoparticles, when the biological uptake processes on the surface of the cell were faster than the physical transport to the cell, the smaller particles were, due to high density, fastest to agglomerate, whereas the larger

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particles stayed mostly unagglomerated and more resistant, and required more time for the body to discard [69]. The familiar case of thalidomide, which was ‘‘proved’’ to be harmless to animals but found to have tragic consequences for pregnant women, shows that benefit in one context could mean harm in another. It is therefore impossible to know or predict the overall effects on the environment of any chemical, and premature generalizations of either great harm or complete safety regarding the introduction of nanomaterials and nanotechnologies must be made with great care [70]. Particles in new environmental surroundings will create new behaviours that are often difficult to predict. Fine particles in the atmosphere are located primarily near the earth’s surface and usually covered with layers of adsorbed water, which increases their catalytic features already promoted by large specific surface areas [71]. Nanoparticles can travel much greater distances by air or in water comparing to microparticles [13]. Various other chemicals are almost equally distributed among the organisms in the biosphere [72], and wide ecosystemic distribution of industrially produced nanoparticles could be expected. Even though the properties and impacts of raw or intermediate materials used to produce nanomaterials might be well known from a risk assessment perspective, the safety risks during manufacturing and the environmental fate of nanomaterials cannot be foreseen with certainty. Despite this, by learning from the experience of previous industrial production, nanotechnologies today have an unprecedented opportunity to evolve into a ‘‘green’’ industry [73]. Due to the enormous complexity of the environment today, it is exceedingly difficult to reach definitive conclusions about the overall effects and consequences of certain materials or technologies on the environment. For example, concerns about the harmful effects of the sun’s UV rays have for some time been resolved by the invention and dissemination of sunscreen agents. However, despite the fact that their use reduces the risk of sunburn, it has never been proved that such use prevents skin cancer in humans. Recently, some have suggested that the use of sunscreens may actually increase the risk, allegedly due to organic chemicals and photoactive particles such as titanium dioxide, which when nanosized can easily penetrate the skin and potentially generate free radicals that might disrupt healthy DNA sequences [16]. Knowing that humans are an extremely adaptive species in the context of the biosphere [74], and that trial-and-error has always been part of evolutionary R&D, feedback-sensitive efforts to resolve any inharmonies in the organization of life should present mechanisms for advancing society on the scientific, ethical, and technological levels. 4.1. A comparison with the case of genetically modified foods Even though the products of biotechnology may present ecological dangers that are more difficult to manage [54], as nanoproducts move from research laboratories into the marketplace it will be necessary to develop precise standards to evaluate the spectrum of their ecological effects. Although this spectrum can never be perfectly projected, the goal should be to study the widest possible range. James Watson has recommended that 3–5% of the funds allocated to bioengineering should be devoted to the study of ethical, legal, and social implications [56]. The case of genetically modified (GM) foods offers a recent and still developing case of the challenges and social impacts that face nanoscience and nanotechnology on their way into industries and markets. Both GM foods and the Human Genome Project have

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contributed to discrepancies between scientific and public opinion. The widespread rejection of GM foods occurred as a result of ethical and social consequences, and it would be well to avoid similar situations as nanotechnologies become an increasingly significant market force. The primary reason for the breakdown of public trust in GM products did not initially arise from public perceptions of health and environmental hazards or impending catastrophes but instead through rash pronouncements and heavy promotion of GM foods and products by large corporations, later shown to be at the expense of broader public interests. The most important lesson from the case of GM foods is that uncertainties should be openly acknowledged. Wide-ranging, inter-disciplinary discussions that include public voices, leading to shared responsibilities and more careful choices, are approaches that acknowledge public attitudes and values and lead to more sustainable solutions. ‘‘An ability to accept uncertainty—to say ‘we’re not sure’—is an essential component of this new approach’’, says James Wilsdon, a proponent of the decision-making approach that does not rely on pure technical criteria alone but strives to take into account as many diverse societal perspectives as possible [13]. Risk assessment of nanoproducts should also follow a direction that ensures that the savings in resource consumption during usage are not offset by increased consumption during manufacture and disposal. And the more ‘‘upstream,’’ culture-friendly, purposedriven, and wise perspectives should not be disregarded in favour of ‘‘downstream’’, more immediate anthropocentric risks and consequences. As part of this approach, the nanoscience research centre at Cambridge University has appointed a lab-based social scientist to focus on the reflection of social values and needs in real-time research practice and guidance [13]. The question of compromise between novelty and incrementality still persists as an important dilemma within nanotech policy. Unlike the case of GM foods, when novelty was insisted upon in order for patents to be granted, but when questions about safety regulations were put forth, substantial equivalence with natural counterparts was claimed, similar tendencies ought to be met with caution, knowing that every nanomaterial and nanoproduct is unique and should not be smuggled down the regulatory pipeline under the guise of generalized etiquette. Since potential damage to humans does not come directly through digestion or contact with GM foods but instead through disrupting naturally diverse ecosystems, a regulatory eye should always be maintained not only on narrow and short-term frames of reference but also on wide-context and long-term influences on the biosphere as a whole. 4.2. Sustainability and harmony with nature Sustainability of nanotechnological methods for the production and functional implementation of nanoparticles presents another major ecological concern. In nature, permanent waste does not exist since waste produced by one species is absorbed as food by others. In contrast, contemporary industrial production processes routinely produce longterm, non-biodegradable wastes. In this sense, the principles of ‘‘green chemistry’’ [75] provide useful guidelines [76–78] for modifying today’s synthesis processes into one that are more sustainable and less waste producing. An orientation towards combining production paths into symbiotic organizations of both small-scale and large-scale production sizes, which could result in zero-waste industrial environments, has been proposed [79–81] as an inspiring possibility on the horizon.

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Many aspects of estimating the viability of methods and procedures for preparing nanostructured materials, and their eventual organization into supra-molecular, multihierarchical structures, should be taken into account. Ordinary physico-chemical analyses should not be the end points of such investigations; consideration should also be given to economic, ecological, and socio-ethical perspectives, including the influence of nanoproducts, the effects of synthesis pathways, resource supply, and the fate of by-products on relevant environments. Since self-replicating nanomachines—the final frontier of the development of nanotechnoscience—tend to copy natural design (namely, the functionality of cellular structures), there are many questions that can be posed concerning the harmonization of nanoscience with nature. For example, if nature never produces absolutely identical entities in its design and self-replication processes (and we have learned that mistakes in replication processes are key to the evolution of life), are tendencies towards perfect uniformity and reproducibility in today’s structural design procedures in harmony with nature? How can man produce perfection via imperfections, as nature does? If nature relies on non-linear systems in which every subsystem changes according to overall changes in the system, should purely top-down, linear, and unilateral hierarchical organizations in human products design cede their places to circular, decentralized, and more feedbackoriented systems? Popular visions of limitless nanotech possibilities are inconsistent with the finity of natural organizations and earth’s resource base. The contemporary problem of population congestion on the planet is on a collision course with an oft-mentioned desire to cure all the world’s illnesses by applying special nanobots in biomedicine treatments that it is hoped would extend man’s lifespan. On the other hand, subtle and long-term changes induced in individual organisms in the presence of potentially toxic substances, are exceedingly difficult to spot and discern from other environmental influences. The lack of evidence concerning the negative health effects of nanoproducts on humans, animals, and/or cell cultures should not be regarded as a sign of their eco-friendliness. Given the impossibility of defining with absolute accuracy the range of effects that certain substances may have on the environment, perhaps all resulting safety announcements should be enclosed within the frame of reserved uncertainty. Human civilization is supported by an inconceivably complex organization of life, and the study of the effects of nanoproducts and nanotechnologies on this foundational web of biological and ecosystemic relationships should not be underestimated for the sake of anthropocentric evaluations of narrowly schematized health effects of nanoproducts on human beings. Natural design processes are typified by the use of (a) relatively simple building blocks; (b) complex environments and complex processes; (c) parallel processing (hundreds of reactions at a time); (d) relatively slow attainment of end states; (e) dealing with subpicomolar quantities; and (f) imperfect reproducibility (overcome by high selectivity for products that meet the required specifications) [82]. By comparison, synthetic methods in chemistry are typified by (a) the use of relatively complex building blocks; (b) simple media and processes; (c) linear reactivity (one reaction at a time); (d) quick attainment of end states (due to far-from-equilibrium conditions); (e) dealing with molar quantities; and (f) a tendency to duplicate reproducibility. Therefore, since natural design and nanoengineering are often regarded as a single organization of creative efforts [83], fundamental biomimicry represents a complex but enormously fruitful challenge for today’s materials science and engineering. Nearly impenetrable abalone shells, flexible and patchy butterfly wings, spider

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threads more rigid than steel, unwettable and self-cleaning lotus leaves, and the skin of dolphins are some examples of products of natural design prepared not by conscious manipulation but by spontaneous, self-organizing processes of nature—and still without comparable counterparts in any laboratory. It has been suggested recently that the only way to solve the so-called ‘‘fat and sticky fingers’’ problem [26] of molecular assembly design is to establish structures reminiscent in functionality of enzymes and rybozomes. However, water is a necessary precondition for such an organization. This does not mean that the fields of bioengineering and nanotechnologies will not some day merge, or that we will eventually learn that along the technological route to improving quality of life and understanding nature, we have been in fact always trying to create or meet something that already exists, namely, our beings and the deepest qualities of life. Thus, humans—after more than four billion years of evolutionary trial-and-error R&D—may be the ultimate nanomachines [84]. In any case, while every novel breakthrough technology normally draws on traditional underpinnings (which through redeployment in a new context acquires new meaning [85]), design visions should naturally move from obscure mechanistic and violent military metaphors towards functional notions that better match the natural order of things [24]. If nanoscience is a trans-disciplinary heading that is evolving into a specific scientific discipline, then holistic, networked, and self-assembled imagery might serve as its paradigm [21,86], in contrast to the manipulative and realistic imagery of the contemporary disciplines of physics, chemistry, and engineering [85]. 5. The quality of scientific research Whereas academic researchers were generally free from external direction until the beginning of the 1970s, the past 30 years has seen a continued increase in R&D investments and an ongoing decrease in global per capita economic growth [87]. Limiting research creativity within the scope of rigid, preconceived objectives, or the pressure to publish in peer-reviewed journals, combined with vague evaluations of the quality of research proposals and project results, have gradually moved aside the sense of personal research responsibility, and may influence the unfavourable drift of research. Conforming to trends that lead to career establishment, instead of focusing on the long-term viability of striving in the largest context of the organization of life, represents the greatest danger in the contemporary scientific society. Animating a sense of responsibility that refers not only to higher authorities but also to deeply rooted ethics within is the major challenge to creative enhancement and truly careful design of modern technologies. Some of the most important steps in the evolution of science, including the discoveries of quantum mechanics, the theory of relativity, and molecular biology of the twentieth century, were not derived from market needs, external demands, or predetermined technoscientific objectives. Rather, many steps came as acts of divine, inwardly turned inspiration from which inexhaustible sources of cognitive, technological, and informational enrichment were found decades later. It has been argued recently that most of the major scientific breakthroughs in the history of science evolved from very little or no funding [88]. But as any researcher knows, it is impossible to directly use the laws of nature to produce a desired object; all that can be done is to set the right limiting conditions and let nature play the recombination part, after which collection, analyses, and further use of outcomes take place. Every process of material and technology design is to some extent self-organizing.

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The fundamentals of nature are never touched; instead, just the tracks upon which her trains are already heading are manipulated. Besides its inner, inherently problematic side, scientific research has its outer, applied, social, and humanistic side as well. The R&D part of scientific work is only one side of the bridge over the river of knowledge; the other side reaches toward the shore of human needs. So one coast of these scientific waters contains the grounds of fundamental physicochemical laws of nature upon which research products are being built; on the other coast, the R&D bridge brings products to society. However, in converting research dreams to reality, the bridge represents a path often named ‘‘nightmare’’ or ‘‘valley of death’’ [89,90], due to its inter-disciplinary, widely contextual character filled with puzzlement, doubt, and risk during the effort to bring R&D creations into social, economic, and ecological daylight. As the laws of nature are never entered into (in the sense that they are never used directly and intentionally in applied scientific design), direct research objectives should to some extent cede their place to open, so-called ‘‘blue skies’’ research [87]—free from externally imposed constraints. On the other side, an orientation towards profitable returns in the market ought to be replaced by a belief that as products are being obtained via selforganization pathways, setting them into social and economic environments will ensure that they find fertile ground—provided they present truly pragmatic, eco- and user-friendly products. In the field of nanoscience, this means that diving into nature’s wonders, and a profound devotion to understanding natural order on a nanoscale, represents the appropriate attitude for fundamental development of future nanotechnology designs. Basic scientific research is oriented towards gaining a fundamental understanding of nature as essential for advancing science and technology forward. When combined with a trial-and-error approach in materials design, every research result becomes equally important to the scientific mind. The importance of trial and error within nanodesign implies that mistakes and ‘‘not-how’’ are as vital as ‘‘know-how’’ on the road to advancing the conceptual network of nanosciences. Every small research, regardless of its immediate or near-term success, stands as an enormously significant potential source of knowledge advancement and innovative achievement. It is my opinion that acknowledging uncertainties in areas where the development of nanoproducts takes place, together with respect for self-organizing natural patterns, offers a far more harmonious plan for unfolding nanoscience and nanotechnology. The truly valuable fruits of human hardships are never immediately seen, often remaining just out of sight beyond the horizon of actual view. Therefore, the tendency of mainstream science to quickly sell nanotech to the financial community, and to collect money from proposed ideas and hoped-for nanodreams, should be undertaken with extreme care and deliberation. The nanotech areas of greatest scientific uncertainty, such as the toxicology of nanoparticles and basic, not-immediately-practical innovations, should not be exempted from funding, even though there is currently only about h5 billion of total global investment in nanotechnologies (with h2 billion coming from private sources) [16] devoted to them. At least 35 countries currently have some kind of national nanotech research programme [14] and, based on experience in the IT field, it has been extrapolated that nanotechnologies have the potential to create seven million jobs in the global market by 2015 [91]. The US National Science Foundation (NSF) predicts that nanotechnology will be a US$1 trillion market within 6–7 years [92]. At the same time, the NSF, while spending

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$8 million on nanotech projects, did not fund a single project that focused on societal implications of nanotechnologies [56]. Whereas citations in scientific databases on nanotechnology follow an almost exponential line of growth, the number of citations on ethics and societal implications shows an almost negligible increase [56]. Since a single nanoscale innovation can span the fields of pharmaceuticals, paints, food, textiles, sports, electronics, telecoms, automotive, and other industries, trans-disciplinary scope and decisions that do not come from strict experts’ views need to be given serious consideration. Areas of current research in self-assemblying syntheses, computational and supramolecular chemistries, genetic and protein engineering, and the scanning-probe manipulation of atoms and molecules need to be intertwined in order to achieve more significant, sustainable progress in developing future nanotechnologies [22]. Only through fostering multi-, inter-, and trans-disciplinary approaches to organizing man’s knowledge and directing programmes of research, can we find the way to nanotechnologies that are inexpensive, sustainable, culture- and eco-friendly, collaborative, freely accessible, and ‘‘open source.’’ 6. Conclusion After studying well-known pathways from new perspectives, insight into new qualities is growing and wiser returns to old paths may be expected. Such is the nature of multidisciplinary approaches to problem solving. By stepping out of the rigid paths being followed, better views of the destinations can be established. Otherwise, the danger remains that we might stay locked in a ‘‘blind spot’’ where we do not see that we do not see. The first step towards improving our knowledge is to see that we do not see—the major point of this paper. Numerous impossibilities, uncertainties, and unknowns within research areas of nanomaterials, nanosciences, and nanotechnologies were discussed. Examples of changes in the initial conditions of experimental observations, which can lead to significant differences in measured outcomes were outlined. I highlighted the complexity of the many environments within which nanosystems appear today. All generalizations concerning their effects on the corresponding media, therefore, need to be taken with special care. Advances in extending mankind’s knowledge and predictability in uncharted territories have been continually present since the word ‘‘nano’’ first appeared in the context of materials science. However, we should be firmly assured that prediction impossibilities, indeterminacies, and ‘‘horizons’’ will remain in the organization of our knowledge. Our work should not be directed towards erasing the unknown by premature generalizations, but instead towards carefully walking the endless line where the coasts of the known and the sea of the unknown meet. Careful guidance in the development of nanotechnologies provides opportunities to spontaneously replace human superimpositions on natural ecosystemic substrates with more harmonious, responsibly feedback-permeated patterns. It was Paul Tillich who said, ‘‘Nature draws straight with curved lines,’’ referring to the well-known fact that natural self-sustaining processes follow non-linear patterns with holistic features [93–95]. In this work, I have described the missing links in a closed loop that connects nanomaterials structures and properties with procedures of placing nanomaterials and nanotechnologies in biological domains and in the context of the overall biospherical web of life. The favourable feature of any cyclical dependency is that taking action on any of their linking

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parts may influence a more harmonious overall flow. It has been acknowledged that searching for the foundations of chemistry led us to the principles of physics. The search for the foundations of physics ends with philosophical discussions that, due to the biological basis of our cognitive apparati, bring us to biological principles. Yet, their detailed considerations turn us to chemical pathways—the beginning of our journey. This work could end with an ancient oriental tale [96] about a stonecutter, as a clever allegory of the circular arrangement of the areas of scientific and humanistic interest in the development of nanomaterials, nanosciences, and nanotechnologies, and of the cyclical pattern of materials and technology design. In the story, a stonecutter, dissatisfied with his life, searches for the fundamental founding principles of life. He becomes the sun first, impressed by its shining constancy. After a time, he realises that clouds can block the sun’s rays. So he changes his mind to become a cloud. Then he realises that clouds are moved too, by the force of wind, so, he decides to become wind. After enjoying being wind for some time, he notices that there is a stone that cannot be moved by his enormous strength, and the man decides to become a stone. Thinking he had finally found the firmest foundation of life, he realised that even then he could be changed by human hands. He turns to them and reveals that it is himself, the stonecutter, who should have always been the most appreciated doer in the creative world. As in this allegory, the design of modern materials and technologies through wise consideration of a wide range of effects on intertwined scientific and humanistic disciplines should become a wonderful story of informative and cognitive enrichment.

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Vuk Uskokovic´ was born in Belgrade, Yugoslavia. He earned a B.Sc. degree from the Faculty of Physical Chemistry at Belgrade University in 2001, and in 2003 was awarded an M.Sc. degree in advanced materials and technologies from the University of Kragujevac, Serbia and Montenegro. From 2002 to 2006, he was with the Advanced Materials Department of the Jozˇef Stefan Institute, Ljubljana, Slovenia. He received a Ph.D. degree from the Jozˇef Stefan International Postgraduate School of Nanosciences and Nanotechnologies in 2006. As of April 2006, he has been with the Center for Advanced Materials Processing of Clarkson University, Potsdam, NY. Besides his devotion to scientific research, he has published shorter works and books comprising discussions that combine the areas of scientific epistemology, ethics, ecology and sociology, with the aim of improving the understanding of current problems in contemporary societies.