Molecular imprinting involves the synthesis of polymers in the presence of a template to produce complementary binding sites with specific recognition ability. The technique has been successfully applied as a measurement and separation technology, producing a uniquely robust and antibody-like polymeric material. Low molecular weight molecules have been extensively exploited as imprint templates, leading to significant achievements in solid-phase extraction, sensing and enzyme-like catalysis. By contrast, macromolecular imprinting remains underdeveloped, principally because of the lack of binding site accessibility. In this review, we focus on the most recent developments in this area, not only covering the widespread use of biological macro-templates but also highlighting the emerging use of synthetic macro-templates, such as dendrimers and hyperbranched polymers.

In this work, the fi rst example of a hierarchically structured hollow silica system is reported without any chemical modifi cation to the enzyme involved in the process. The leaching of the physically adsorbed enzyme is substantially restrained in comparison to pure hollow silica supports. The hierarchical architecture is composed of the ordered hollow silica spheres with a shellin-shell structure. This rationally integrated architecture, which serves as the host for glucose oxidase immobilization, displays many signifi cant advantages, including increases in mechanical stability, enzyme loading, and bioactivity, and a decrease in enzyme leaching compared to existing pure hollow silica matrices. This facilitates further multifarious applications for enhanced enzyme immobilization, biosensors, and biocatalysis.

Molecular imprinting has attracted considerable attention, because it offers the tantalising prospect of specific antibody-mimicking recognition and binding sites, coupled with several distinct advantages such as excellent stability, ease of preparation and low cost. In this Minireview, recent progress in molecularly imprinted sorbent assays is discussed, with a particular emphasis on the most significant developments and applications over the last few years.

Chemical functionalization broadens carbon nanotube (CNT) applications, conferring new functions, but at the same time potentially altering toxicity. Although considerable experimental data related to CNT toxicity, at the molecular and cellular levels, have been reported, there is very limited information available for the corresponding mechanism involved (e.g. cell apoptosis and genotoxicity). The threshold dose for safe medical application in relation to both pristine and functionalized carbon nanotubes remains ambiguous. In this study, we evaluated the in vitro cytotoxicity of pristine and functionalized (–OH, –COOH) multi-walled carbon nanotubes (MWCNTs) for cell viability, oxidant detection, apoptosis and DNA mutations, to determine the nontoxic dose and influence of functional group in a human lung-cancer cell line exposed to 1–1000 μg/ml MWCNTs for 24, 48 and 72 h. The findings suggest that pristine MWCNTs induced more cell death than functionalized MWCNTs while functionalized MWCNTs are more genotoxic compared to their pristine form. The level of both dose and dispersion in the matrix used should be taken into consideration before applying further clinical applications of MWCNTs.

A catalytic and positively thermosensitive molecularly imprinted polymer is reported. This unique imprinted polymer was composed of 4‐nitrophenyl phosphate‐imprinted networks that exhibited a thermosensitive interpolymer interaction between poly(2‐trifluoromethylacrylic acid) (PTFMA) and poly(1‐vinylimidazole) (PVI), which contains catalytically active sites. At a relatively low temperature (such as 20 °C), this imprinted polymer did not demonstrate significant catalytic activity for the hydrolysis of 4‐nitrophenyl acetate due to the interpolymer complexation between PVI and PTFMA, which blocked access to the active sites of PVI and caused shrinking of the polymer. Conversely, at higher temperatures (such as 40 °C), this polymer showed significant catalytic activity resulting from the dissociation of the interpolymer complexes between PVI and PTFMA, which facilitated access to the active sites of PVI and inflated the polymer. Unlike previously reported poly(N‐isopropylacrylamide)‐based molecularly imprinted polymers, which demonstrated decreased molecular recognition and catalytic activity with increased temperatures, i.e., negatively thermosensitive molecular recognition and catalysis abilities, this imprinted polymer exploits the unique interpolymer interaction between PVI and PTFMA, enabling the reversed thermal responsiveness.

An originally designed temperature-responsive nanoreactor is reported. The nanoreactor is made of Ag nanoparticles and a functional polymer composite of poly(acrylamide) (PAAm) and poly(2-acrylamide-2-methylpropanesulfonic acid) (PAMPS). At a relatively low temperature (e.g., 20 °C), this nanoreactor displayed weak reactivity because of the interpolymer complexation between PAAm and PAMPS, which largely restricted the access of reactants to the encapsulated Ag nanoparticles. On the contrary, at a relatively high temperatures (e.g., 40 °C), the nanoreactor demonstrated significant catalytic activity resulting from the dissociation of the interpolymer complexation between PAAm and PAMPS, which allowed reactants to get access to the encapsulated Ag nanoparticles. By taking account of previously reported PNIPAm-based nanoreactors, which show inverse temperature response, i.e., reactivity decreases whilst temperature increases, this temperature-responsive nanoreactor would greatly facilitate and enrich the increasing studies on smart nanomaterials, generating numerous applications in a wide range of areas, such as catalysis and sensing.

The use of the molecular imprinting technique to produce polymers with high specificity for a given "molecular template" has undergone a rapid and expansive evolution since the inception of the idea over half a century ago. It was only a matter of time before the seemingly inevitable "marriage" of this concept with another modern research obsession, the generation of "smart" polymers, capable of reacting quickly, accurately and reproducibly to changes in their environment. Many advances have since been made, concerning the quality and diversity of these systems and polymers responsive to temperature, pH and a host of other environmental cues now exist. This article provides a succinct overview of the process and outcomes of "smart" molecular imprinting, followed by a detailed assessment of recent developments and applications in such field.

The single step synthesis of an Fe(II) porphyrin cored hyperbranched polymer, possessing similar size and topology to the natural heme containing proteins, is reported: UV spectroscopy successfully demonstrated the ability of this polymer to reversibly bind oxygen.