Nanochemistry

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Nanochemistry is an emerging sub-discipline of the chemical and material sciences that deals with the development of new methods for creating nanoscale materials. [1] The term "nanochemistry" was first used by Ozin in 1992 as 'the uses of chemical synthesis to reproducibly afford nanomaterials from the atom "up", contrary to the nanoengineering and nanophysics approach that operates from the bulk "down"'. [2] Nanochemistry focuses on solid-state chemistry that emphasizes synthesis of building blocks that are dependent on size, surface, shape, and defect properties, rather than the actual production of matter. Atomic and molecular properties mainly deal with the degrees of freedom of atoms in the periodic table. However, nanochemistry introduced other degrees of freedom that controls material's behaviors by transformation into solutions. [3] Nanoscale objects exhibit novel material properties, largely as a consequence of their finite small size. Several chemical modifications on nanometer-scaled structures approve size dependent effects. [2]

Contents

Selenium Nanoparticles Selenium NPs.jpg
Selenium Nanoparticles

Nanochemistry is used in chemical, materials and physical science as well as engineering, biological, and medical applications. Silica, gold, polydimethylsiloxane, cadmium selenide, iron oxide, and carbon are materials that show its transformative power. Nanochemistry can make the most effective contrast agent of MRI out of iron oxide (rust) which can detect cancers and kill them at their initial stages. [4] Silica (glass) can be used to bend or stop lights in their tracks. [5] Developing countries also use silicone to make circuits for the fluids used in pathogen detection. [6] Nano-construct synthesis leads to the self-assembly of the building blocks into functional structures that may be useful for electronic, photonic, medical, or bioanalytical problems. Nanochemical methods can be used to create carbon nanomaterials such as carbon nanotubes, graphene, and fullerenes which have gained attention in recent years due to their remarkable mechanical and electrical properties. [7]

Applications

Medicine

Magnetic Resonance Imaging Detection (MDR)

Over the past two decades, iron oxide nanoparticles for biomedical use had increased dramatically, largely due to its ability of non-invasive imaging, targeting and triggering drug release, or cancer therapy. Stem or immune cell could be marked with iron oxide nanoparticles to be detected by Magnetic resonance imaging (MDR). However, the concentration of iron oxide nanoparticles needs to be high enough to enable the significant detection by MDR. [4] Due to the limited understanding of physicochemical nature of iro oxide nanoparticles in biological systems, more research is needed to ensure nanoparticles can be controlled under certain conditions for medical usage without posing harm to human. [8]

Drug delivery

Emerging methods of drug delivery involving nanotechnological methods can be useful by improving bodily response, specific targeting, and non-toxic metabolism. Many nanotechnological methods and materials can be functionalized for drug delivery. Ideal materials employ a controlled-activation nanomaterial to carry a drug cargo into the body. Mesoporous silica nanoparticles (MSN) have increased in research popularity due to their large surface area and flexibility for various individual modifications while maintaining high-resolution performance under imaging techniques. [9] Activation methods greatly vary across nanoscale drug delivery molecules, but the most commonly used activation method uses specific wavelengths of light to release the cargo. Nanovalve-controlled cargo release uses low-intensity light and plasmonic heating to release the cargo in a variation of MSN containing gold molecules. [10] The two-photon activated photo-transducer (2-NPT) uses near infrared wavelengths of light to induce the breaking of a disulfide bond to release the cargo. [11] Recently, nanodiamonds have demonstrated potential in drug delivery due to non-toxicity, spontaneous absorption through the skin, and the ability to enter the blood–brain barrier.

The unique structure of carbon nanotubes also gives rise to many innovative inventions of new medical methods. As more medicine is made at the nano level to revolutionize the ways for human to detect and treat diseases, carbon nanotubes become a stronger candidate in new detection methods [12] and therapeutic strategies. [13] Specially, carbon nanotubes can be transformed into sophisticated biomolecule and allow its detection through changes in the carbon nanotube fluorescence spectra. [14] Also, carbon nanotubes can be designed to match the size of small drug and endocitozed by a target cell, hence becoming a delivery agent. [15]

Tissue engineering

Cells are very sensitive to nanotopographical features, so optimization of surfaces in tissue engineering has pushed towards implantation. Under appropriate conditions, a carefully crafted 3-dimensional scaffold is used to direct cell seeds toward artificial organ growth. The 3-D scaffold incorporates various nanoscale factors that control the environment for optimal and appropriate functionality. [16] The scaffold is an analog of the in vivo extracellular matrix in vitro, allowing for successful artificial organ growth by providing the necessary, complex biological factors in vitro.

Wounds healing

For abrasions and wounds, nanochemistry has demonstrated applications in improving the healing process. Electrospinning is a polymerization method used biologically in tissue engineering but can also be used for wound dressing and drug delivery. This produces nanofibers that encourage cell proliferation, antibacterial properties, in controlled environment. [17] These properties appear macroscopically, however, nanoscale versions may show improved efficiency due to nanotopographical features. Targeted interfaces between nanofibers and wounds have higher surface area interactions and are advantageous in vivo. [18] There is evidence that certain nanoparticles of silver are useful to inhibit some viruses and bacteria. [19]

Cosmetics

Zinc oxide nanoparticles Zinc oxide nanoparticles crop.png
Zinc oxide nanoparticles
Titanium dioxide nanoparticles Titanium dioxide nanoparticles.png
Titanium dioxide nanoparticles

Materials in certain cosmetics such as sun cream, moisturizer, and deodorant may have potential benefits from the use of nanochemistry. Manufacturers are working to increase the effectiveness of various cosmetics by facilitating oil nanoemulsion. [20] These particles have extended the boundaries in managing wrinkling, dehydrated, and inelastic skin associated with aging. In sunscreen, titanium dioxide and zinc oxide nanoparticles prove to be effective UV filters but can also penetrate through skin. [21] These chemicals protect the skin against harmful UV light by absorbing or reflecting the light and prevent the skin from retaining full damage by photoexcitation of electrons in the nanoparticle. [22]

Electrics

Nanowire compositions

Scientists have devised a large number of nanowire compositions with controlled length, diameter, doping, and surface structure by using vapor and solution phase strategies. These oriented single crystals are being used in semiconductor nanowire devices such as diodes, transistors, logic circuits, lasers, and sensors. Since nanowires have a one-dimensional structure, meaning a large surface-to-volume ratio, the diffusion resistance decreases. In addition, their efficiency in electron transport which is due to the quantum confinement effect, makes their electrical properties be influenced by minor perturbation. [23] Therefore, the use of these nanowires in nanosensor elements increases the sensitivity in electrode response. As mentioned above, the one-dimensionality and chemical flexibility of the semiconductor nanowires make them applicable in nanolasers. Peidong Yang and his co-workers have done some research on the room-temperature ultraviolet nanowires used in nanolasers. They have concluded that using short wavelength nanolasers has applications in different fields such as optical computing, information storage, and microanalysis. [24]

Catalysis

Nanoenzymes (or nanozymes)

The small size of nanoenzymes (or nanozymes) (1–100 nm) has provided them with unique optical, magnetic, electronic, and catalytic properties. [25] Moreover, the control of surface functionality of nanoparticles and the predictable nanostructure of these small-sized enzymes have allowed them to create a complex structure on their surface that can meet the needs of specific applications [26]

Research areas

Nanodiamonds

Synthesis

Fluorescent nanoparticles are highly sought after. They have broad applications, but their use in macroscopic arrays allows them efficient in applications of plasmonics, photonics, and quantum communications. While there are many methods in assembling nanoparticles array, especially gold nanoparticles, they tend to be weakly bonded to their substrate so they can't be used for wet chemistry processing steps or lithography. Nanodiamonds allow for greater variability in access that can subsequently be used to couple plasmonic waveguides to realize quantum plasmonic circuitry.

Fluorescent nanodiamonds surrounding living HeLa cells Fluorescent nanodiamonds surrounding living HeLa cells.jpg
Fluorescent nanodiamonds surrounding living HeLa cells

Nanodiamonds can be synthesized by employing nanoscale carbonaceous seeds created in a single step by using a mask-free electron beam-induced position technique to add amine groups. This assembles nanodiamonds into an array. The presence of dangling bonds at the nanodiamond surface allows them to be functionalized with a variety of ligands. The surfaces of these nanodiamonds are terminated with carboxylic acid groups, enabling their attachment to amine-terminated surfaces through carbodiimide coupling chemistry. [27] This process affords a high yield that relies on covalent bonding between the amine and carboxyl functional groups on amorphous carbon and nanodiamond surfaces in the presence of EDC. Thus unlike gold nanoparticles, they can withstand processing and treatment, for many device applications.

Fluorescent (nitrogen vacancy)

Fluorescent properties in nanodiamonds arise from the presence of nitrogen-vacancy (NV) centers, nitrogen atoms next to a vacancy. Fluorescent nanodiamond (FND) was invented in 2005 and has since been used in various fields of study. [28] The invention received a US patent in 2008 States7326837 B2 United States 7326837 B2,Chau-Chung Han; Huan-Cheng Chang& Shen-Chung Leeet al.,"Clinical applications of crystalline diamond particles",issued February 5, 2008, assigned to Academia Sinica, Taipei (TW) , and a subsequent patent in 2012 States8168413 B2 United States 8168413 B2,Huan-Cheng Chang; Wunshian Fann& Chau-Chung Han,"Luminescent Diamond Particles",issued May 1, 2012, assigned to Academia Sinica, Taipei (TW) . NV centers can be created by irradiating nanodiamonds with high-energy particles (electrons, protons, helium ions), followed by vacuum-annealing at 600–800°C. Irradiation forms vaccines in the diamond structure while vacuum-annealing migrates these vacancies, which will get trapped by nitrogen atoms within the nanodiamond. This process produces two types of NV centers. Two types of NV centers are formed—neutral (NV0) and negatively charged (NV–)—and these have different emission spectra. The NV– the center is of particular interest because it has an S = 1 spin ground state that can be spin-polarized by optical pumping and manipulated using electron paramagnetic resonance. [29] Fluorescent nanodiamonds combine the advantages of semiconductor quantum dots (small size, high photostability, bright multicolor fluorescence) with biocompatibility, non-toxicity, and rich surface chemistry, which means that they have the potential to revolutionize Vivo imaging applications. [30]

Drug-delivery and biological compatibility

Nanodiamonds can self-assemble and a wide range of small molecules, proteins antibodies, therapeutics, and nucleic acids can bind to its surface allowing for drug delivery, protein-mimicking, and surgical implants. Other potential biomedical applications are the use of nanodiamonds as support for solid-phase peptide synthesis and as sorbents for detoxification and separation and fluorescent nanodiamonds for biomedical imaging. Nanodiamonds are capable of biocompatibility, the ability to carry a broad range of therapeutics, dispersibility in water and scalability, and the potential for targeted therapy all properties needed for a drug delivery platform. The small size, stable core, rich surface chemistry, ability to self-assemble, and low cytotoxicity of nanodiamonds have led to suggestions that they could be used to mimic globular proteins. Nanodiamonds have been mostly studied as potential injectable therapeutic agents for generalized drug delivery, but it has also been shown that films of Parylene nanodiamond composites can be used for localized sustained release of drugs over periods ranging from two days to one month. [31]

Nanolithography

Nanolithography is the technique to pattern materials and build devices under nano-scale. Nanolithography is often used together with thin-film-deposition, self-assembly, and self-organization techniques for various nanofabrications purpose. Many practical applications make use of nanolithography, including semiconductor chips in computers. There are many types of nanolithography, which include:

Each nanolithography technique has varying factors of the resolution, time consumption, and cost. There are three basic methods used by nanolithography. One involves using a resist material that acts as a "mask", known as photoresists, to cover and protect the areas of the surface that are intended to be smooth. The uncovered portions can now be etched away, with the protective material acting as a stencil. The second method involves directly carving the desired pattern. Etching may involve using a beam of quantum particles, such as electrons or light, or chemical methods such as oxidation or Self-assembled monolayers. The third method places the desired pattern directly on the surface, producing a final product that is ultimately a few nanometers thicker than the original surface. To visualize the surface to be fabricated, the surface must be visualized by a nano-resolution microscope, which includes the scanning probe microscopy and the atomic force microscope. Both microscopes can also be engaged in processing the final product.

Negative photoresist Negative photoresist.png
Negative photoresist
Positive photoresist Positive photoresist.png
Positive photoresist

Photoresists

Photoresists are light-sensitive materials, composed of a polymer, a sensitizer, and a solvent. Each element has a particular function. The polymer changes its structure when it is exposed to radiation. The solvent allows the photoresist to be spun and to form thin layers over the wafer surface. Finally, the sensitizer, or inhibitor, controls the photochemical reaction in the polymer phase. [32]

Photoresists can be classified as positive or negative. In positive photoresists, the photochemical reaction that occurs during exposure, weakens the polymer, making it more soluble to the developer so the positive pattern is achieved. Therefore, the masks contains an exact copy of the pattern, which is to remain on the wafer, as a stencil for subsequent processing. In the case of negative photoresists, exposure to light causes the polymerization of the photoresist so the negative resist remains on the surface of the substrate where it is exposed, and the developer solution removes only the unexposed areas. Masks used for negative photoresists contain the inverse or photographic “negative” of the pattern to be transferred. Both negative and positive photoresists have their own advantages. The advantages of negative photoresists are good adhesion to silicon, lower cost, and a shorter processing time. The advantages of positive photoresists are better resolution and thermal stability. [32]

Nanometer-size clusters

Monodisperse, nanometer-size clusters (also known as nanoclusters) are synthetically grown crystals whose size and structure influence their properties through the effects of quantum confinement. One method of growing these crystals is through inverse micellar cages in non-aqueous solvents. [33] Research conducted on the optical properties of MoS2 nanoclusters compared them to their bulk crystal counterparts and analyzed their absorbance spectra. The analysis reveals that size dependence of the absorbance spectrum by bulk crystals is continuous, whereas the absorbance spectrum of nanoclusters takes on discrete energy levels. This indicates a shift from solid-like to molecular-like behavior which occurs at a reported cluster the size of 4.5 – 3.0 nm. [33]

Interest in the magnetic properties of nanoclusters exists due to their potential use in magnetic recording, magnetic fluids, permanent magnets, and catalysis. Analysis of Fe clusters shows behavior consistent with ferromagnetic or superparamagnetic behavior due to strong magnetic interactions within clusters. [33]

Dielectric properties of nanoclusters are also a subject of interest due to their possible applications in catalysis, photocatalysis, micro capacitors, microelectronics, and nonlinear optics. [34]

Nanothermodynamics

The idea of nanothermodynamics was initially proposed by T. L. Hill in 1960, theorizing the differences between differential and integral forms of properties due to small sizes. The size, shape, and environment of a nanoparticle affect the power law, or its proportionality, between nano and macroscopic properties. Transitioning from macro to nano changes the proportionality from exponential to power. [35] Therefore, nanothermodynamics and the theory of statistical mechanics are related in concept. [36]

Notable researchers

There are several researchers in nanochemistry that have been credited with the development of the field. Geoffrey A. Ozin, from the University of Toronto, is known as one of the "founding fathers of Nanochemistry" due to his four and a half decades of research on this subject. [37] This research includes the study of matrix isolation laser Raman spectroscopy, naked metal clusters chemistry and photochemistry, nanoporous materials, hybrid nanomaterials, mesoscopic materials, and ultrathin inorganic nanowires. [38]

Another chemist who is also viewed as one of the nanochemistry's pioneers is Charles M. Lieber at Harvard University. He is known for his contributions to the development of nano-scale technologies, particularly in the field of biology and medicine. [39] The technologies include nanowires, a new class of quasi-one-dimensional materials that have demonstrated superior electrical, optical, mechanical, and thermal properties and can be used potentially as biological sensors. Research under Lieber has delved into the use of nanowires mapping brain activity. [40]

Shimon Weiss, a professor at the University of California, Los Angeles, is known for his research of fluorescent semiconductor nanocrystals, a subclass of quantum dots, for biological labeling. [41]

Paul Alivisatos, from the University of California, Berkeley, is also notable for his research on the fabrication and use of nanocrystals. This research has the potential to develop insight into the mechanisms of small-scale particles such as the process of nucleation, cation exchange, and branching. A notable application of these crystals is the development of quantum dots. [42]

Peidong Yang, another researcher from the University of California, Berkeley, is also notable for his contributions to the development of 1-dimensional nanostructures. The Yang group has active research projects in the areas of nanowire photonics, nanowire-based solar cells, nanowires for solar to fuel conversion, nanowire thermoelectrics, nanowire-cell interface, nanocrystal catalysis, nanotube nanofluidics, and plasmonics. [43]

Related Research Articles

<span class="mw-page-title-main">Nanotechnology</span> Field of science involving control of matter on atomic and (supra)molecular scales

Nanotechnology was defined by the National Nanotechnology Initiative as the manipulation of matter with at least one dimension sized from 1 to 100 nanometers (nm). At this scale, commonly known as the nanoscale, surface area and quantum mechanical effects become important in describing properties of matter. The definition of nanotechnology is inclusive of all types of research and technologies that deal with these special properties. It is therefore common to see the plural form "nanotechnologies" as well as "nanoscale technologies" to refer to the broad range of research and applications whose common trait is size. An earlier description of nanotechnology referred to the particular technological goal of precisely manipulating atoms and molecules for fabrication of macroscale products, also now referred to as molecular nanotechnology.

Nanomedicine is the medical application of nanotechnology. Nanomedicine ranges from the medical applications of nanomaterials and biological devices, to nanoelectronic biosensors, and even possible future applications of molecular nanotechnology such as biological machines. Current problems for nanomedicine involve understanding the issues related to toxicity and environmental impact of nanoscale materials.

Nanosensors are nanoscale devices that measure physical quantities and convert these to signals that can be detected and analyzed. There are several ways proposed today to make nanosensors; these include top-down lithography, bottom-up assembly, and molecular self-assembly. There are different types of nanosensors in the market and in development for various applications, most notably in defense, environmental, and healthcare industries. These sensors share the same basic workflow: a selective binding of an analyte, signal generation from the interaction of the nanosensor with the bio-element, and processing of the signal into useful metrics.

<span class="mw-page-title-main">Nanomaterials</span> Materials whose granular size lies between 1 and 100 nm

Nanomaterials describe, in principle, materials of which a single unit is sized between 1 and 100 nm.

<span class="mw-page-title-main">Nanocomposite</span> Solid material with nano-scale structure

Nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm) or structures having nano-scale repeat distances between the different phases that make up the material.

Nanoelectronics refers to the use of nanotechnology in electronic components. The term covers a diverse set of devices and materials, with the common characteristic that they are so small that inter-atomic interactions and quantum mechanical properties need to be studied extensively. Some of these candidates include: hybrid molecular/semiconductor electronics, one-dimensional nanotubes/nanowires or advanced molecular electronics.

Nanotoxicology is the study of the toxicity of nanomaterials. Because of quantum size effects and large surface area to volume ratio, nanomaterials have unique properties compared with their larger counterparts that affect their toxicity. Of the possible hazards, inhalation exposure appears to present the most concern, with animal studies showing pulmonary effects such as inflammation, fibrosis, and carcinogenicity for some nanomaterials. Skin contact and ingestion exposure are also a concern.

<span class="mw-page-title-main">Biointerface</span>

A biointerface is the region of contact between a biomolecule, cell, biological tissue or living organism or organic material considered living with another biomaterial or inorganic/organic material. The motivation for biointerface science stems from the urgent need to increase the understanding of interactions between biomolecules and surfaces. The behavior of complex macromolecular systems at materials interfaces are important in the fields of biology, biotechnology, diagnostics, and medicine. Biointerface science is a multidisciplinary field in which biochemists who synthesize novel classes of biomolecules cooperate with scientists who have developed the tools to position biomolecules with molecular precision, scientists who have developed new spectroscopic techniques to interrogate these molecules at the solid-liquid interface, and people who integrate these into functional devices. Well-designed biointerfaces would facilitate desirable interactions by providing optimized surfaces where biological matter can interact with other inorganic or organic materials, such as by promoting cell and tissue adhesion onto a surface.

The following outline is provided as an overview of and topical guide to nanotechnology:

Polymer nanocomposites (PNC) consist of a polymer or copolymer having nanoparticles or nanofillers dispersed in the polymer matrix. These may be of different shape, but at least one dimension must be in the range of 1–50 nm. These PNC's belong to the category of multi-phase systems that consume nearly 95% of plastics production. These systems require controlled mixing/compounding, stabilization of the achieved dispersion, orientation of the dispersed phase, and the compounding strategies for all MPS, including PNC, are similar. Alternatively, polymer can be infiltrated into 1D, 2D, 3D preform creating high content polymer nanocomposites.

Green nanotechnology refers to the use of nanotechnology to enhance the environmental sustainability of processes producing negative externalities. It also refers to the use of the products of nanotechnology to enhance sustainability. It includes making green nano-products and using nano-products in support of sustainability.

<span class="mw-page-title-main">Nanodiamond</span> Extremely small diamonds used for their thermal, mechanical and optoelectronic properties

Nanodiamonds, or diamond nanoparticles, are diamonds with a size below 100 nanometers. They can be produced by impact events such as an explosion or meteoritic impacts. Because of their inexpensive, large-scale synthesis, potential for surface functionalization, and high biocompatibility, nanodiamonds are widely investigated as a potential material in biological and electronic applications and quantum engineering.

Self-assembling peptides are a category of peptides which undergo spontaneous assembling into ordered nanostructures. Originally described in 1993, these designer peptides have attracted interest in the field of nanotechnology for their potential for application in areas such as biomedical nanotechnology, tissue cell culturing, molecular electronics, and more.

<span class="mw-page-title-main">Nanofountain probe</span>

A nanofountain probe (NFP) is a device for 'drawing' micropatterns of liquid chemicals at extremely small resolution. An NFP contains a cantilevered micro-fluidic device terminated in a nanofountain. The embedded microfluidics facilitates rapid and continuous delivery of molecules from the on-chip reservoirs to the fountain tip. When the tip is brought into contact with the substrate, a liquid meniscus forms, providing a path for molecular transport to the substrate. By controlling the geometry of the meniscus through hold time and deposition speed, various inks and biomolecules could be patterned on a surface, with sub 100 nm resolution.

<span class="mw-page-title-main">Nanoparticle–biomolecule conjugate</span> Tailored macromolecule with covalently-bonded bio-active substances targeting specific tissues

A nanoparticle–biomolecule conjugate is a nanoparticle with biomolecules attached to its surface. Nanoparticles are minuscule particles, typically measured in nanometers (nm), that are used in nanobiotechnology to explore the functions of biomolecules. Properties of the ultrafine particles are characterized by the components on their surfaces more so than larger structures, such as cells, due to large surface area-to-volume ratios. Large surface area-to-volume-ratios of nanoparticles optimize the potential for interactions with biomolecules.

The applications of nanotechnology, commonly incorporate industrial, medicinal, and energy uses. These include more durable construction materials, therapeutic drug delivery, and higher density hydrogen fuel cells that are environmentally friendly. Being that nanoparticles and nanodevices are highly versatile through modification of their physiochemical properties, they have found uses in nanoscale electronics, cancer treatments, vaccines, hydrogen fuel cells, and nanographene batteries.

<span class="mw-page-title-main">Chemiresistor</span>

A chemiresistor is a material that changes its electrical resistance in response to changes in the nearby chemical environment. Chemiresistors are a class of chemical sensors that rely on the direct chemical interaction between the sensing material and the analyte. The sensing material and the analyte can interact by covalent bonding, hydrogen bonding, or molecular recognition. Several different materials have chemiresistor properties: metal-oxide semiconductors, some conductive polymers, and nanomaterials like graphene, carbon nanotubes and nanoparticles. Typically these materials are used as partially selective sensors in devices like electronic tongues or electronic noses.

<span class="mw-page-title-main">Cobalt oxide nanoparticle</span>

In materials and electric battery research, cobalt oxide nanoparticles usually refers to particles of cobalt(II,III) oxide Co
3O
4 of nanometer size, with various shapes and crystal structures.

<span class="mw-page-title-main">Carbon quantum dot</span>

Carbon quantum dots also commonly called carbon nano dots are carbon nanoparticles which are less than 10 nm in size and have some form of surface passivation.

Niveen M. Khashab is a Lebanese chemist and an associate Professor of chemical Sciences and engineering at King Abdullah University of Science and Technology in Saudi Arabia since 2009. She is a laureate of the 2017 L'Oréal-UNESCO Awards for Women in Science "for her contributions to innovative smart hybrid materials aimed at drug delivery and for developing new techniques to monitor intracellular antioxidant activity." She is also a fellow of the Royal Chemical Society, and a member of the American Chemical Society.

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