With recent advances in mesostructured materials and nanotechnologies, new methods are emerging to design optical sensors and biosensors, and to develop highly sensitive solid sensors. Here, highly sensitive, low cost, simple nanosensor designs for naked‐eye detection of toxic metal ions are successfully developed by the immobilization of commercially available α,β,γ,δ‐tetrakis(1‐methylpyridinium‐4‐yl)porphine p‐toluenesulfonate (TMPyP) and diphenylcarbazide (DPC), and chemically synthesized 4‐n‐dodecyl‐6‐(2‐thiazolylazo) resorcinol (DTAR) and 4‐n‐dodecyl‐6‐(2‐pyridylazo) phenol (DPAP) chromophore molecules into spherical nanosized cavities and surfaces. A rational strategy was crucial to develop optical nanosensors that can be used to control accurate recognition and signaling abilities of analyte species for ion‐sensing purposes. This is the first reported evidence of the significant key factors of the development of receptors as ‘indicator dyes' and surface‐confinement materials as ‘carriers' to broadening the applicability of optical chemical sensors for selective discrimination of trace levels of toxic analytes. In all the nanosensor design techniques presented here, a dense pattern of immobilized hydrophobic ‘neutral' and hydrophilic ‘charged' chromophores with intrinsic mobility, as a result of extremely robust constructed sequences on nanoscale structures, is a key to enhancing the sensing functionality of optical nanosensors. These nanosensor designs can be used as cage probe sinks with reliable control, for the first time, over the colorimetric recognition of cadmium ions to low levels of concentration in the range of 10–9 to 10–10 M. Optimization of control sensing conditions is established to achieve enhanced signal response and color intensities. These chemical nanosensors are reversible and have the potential to serve effectively in on‐site field analysis of environmental samples, which eliminates the necessity for instrument‐dependent analysis. Moreover, these new classes of optical cage sensors exhibit long‐term stability of signaling and recognition functionalities that in general provide extraordinary sensitivity, selectivity, reusability, and fast kinetic detection and quantification of various deleterious metal ions in our environment.

Large-scale cubic Pm3n silica monoliths (HOM) were fabricated in wormhole and ordered mesostructures and in shape- and size-controlled cage pores by using a simple and fast strategy. The functional use of these 3D HOM monoliths as probe anchoring templates enabled the efficient designs of optical nanosensors. In this regard, the synthesized chromoionophore was physisorbed into the 3D HOM pore surface carriers without potential leaching. Results revealed that the structural features of the HOM monoliths such as ordered and worm-like cage pores substantially influenced the ion-sensing functionality in terms of their probe inclusion capacities, ion-transport diffusion, optical responsive profile, and visual color transition series during the detection of ultratraces of toxic Pb(II) ions. The nanosensors were selective in discriminating trace Pb(II) ions over multicomponent matrix species, with reliable and reproducible detection and quantification limits. A comparative study on the ion-sensing efficiency of the chromoionophore in both solution and solid phases indicated that the solid HOM monoliths show promise as probe templates to design-made nanosensors for the detection of ultratraces Pb(II) ions. Considering the environmental factors, nanosensors were solvent-free systems and had the capacity to serve as ion preconcentrators with complete reversibility and reusability. The significant features of the probe-design nanosensors led to overcoming the disposal problems, which were normally associated with the liquid probe systems.

A shallow-to-deep instability of hydrogen defect centres in narrow-gap oxide semiconductors is revealed by a study of the electronic structure and electrical activity of their muonium counterparts, a methodology that we term ‘muonics’. In CdO, Ag2O and Cu2O, paramagnetic muonium centres show varying degrees of delocalization of the singly occupied orbital, their hyperfine constants spanning 4 orders of magnitude. PbO and RuO2, on the other hand, show only electronically diamagnetic muon states, mimicking those of interstitial protons. Muonium in CdO shows shallow-donor behaviour, dissociating between 50 and 150 K; the effective ionization energy of 0.1 eV is at some variance with the effective-mass model but illustrates the possibility of hydrogen doping, inducing n-type conductivity as in the wider-gap oxide, ZnO. For Ag2O, the principal donor level is deeper (0.25 eV) but ionization is nonetheless complete by room temperature. Striking examples of level-crossing and RF resonance spectroscopy reveal a more complex interplay of several metastable states in this case. In Cu2O, muonium has quasi-atomic character and is stable to 600 K, although the electron orbital is substantially more delocalized than in the trapped-atom states known in certain wide-gap dielectric oxides. Its eventual disappearance towards 900 K, with an effective ionization energy of 1 eV, defines an electrically active level near mid-gap in this material.

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