This tutorial review provides an outlook on nanomaterials that are currently being used for theranostic purposes, with a special focus on mesoporous silica nanoparticle (MSNP) based materials. MSNPs with large surface area and pore volume can serve as efficient carriers for various therapeutic agents. The functionalization of MSNPs with molecular, supramolecular or polymer moieties, provides the material with great versatility while performing drug delivery tasks, which makes the delivery process highly controllable. This emerging area at the interface of chemistry and the life sciences offers a broad palette of opportunities for researchers with interests ranging from sol-gel science, the fabrication of nanomaterials, supramolecular chemistry, controllable drug delivery and targeted theranostics in biology and medicine.
A template-directed protocol, which capitalizes on donor-acceptor interactions, is employed to synthesize a semi-rigid cyclophane (ExBox(4+)) that adopts a box-like geometry and is comprised of π-electron-poor 1,4-phenylene-bridged ("extended") bipyridinium units (ExBIPY(2+)). ExBox(4+) functions as a high-affinity scavenger of an array of different polycyclic aromatic hydrocarbons (PAHs), ranging from two to seven fused rings, as a result of its large, accommodating cavity (approximately 3.5 Å in width and 11.2 Å in length when considering the van der Waals radii) and its ability to form strong non-covalent bonding interactions with π-electron-rich PAHs in either organic or aqueous media. In all, 11 PAH guests were observed to form inclusion complexes with ExBox(4+), with coronene being the largest included guest. Single-crystal X-ray diffraction data for the 11 inclusion complexes ExBox(4+)⊂PAH as well as UV/vis spectroscopic data for 10 of the complexes provide evidence of the promiscuity of ExBox(4+) for the various PAHs. Nuclear magnetic resonance spectroscopy and isothermal titration calorimetric analyses of 10 of the inclusion complexes are employed to further characterize the host-guest interactions in solution and determine the degree with which ExBox(4+) binds each PAH compound. As a proof-of-concept, a batch of crude oil from Saudi Arabia was subjected to extraction with the water-soluble form of the PAH receptor, ExBox·4Cl, resulting in the isolation of different aromatic compounds after ExBox·4Cl was regenerated.
A uniform and crack-free metal−organic framework (MOF) thin film composed of free-standing acicular nanorods was grown on a transparent conducting glass substrate. The MOF thin film exhibits electrochromic switching between yellow and deep blue by means of a one-electron redox reaction at its pyrene-based linkers. The rigid MOF stabilizes the radical cations of the pyrene linkers at positive applied potential, resulting in the reversible color change of the MOF film. The regular and uniform channels of the MOF allow ions to migrate through the entire film. The MOF thin film thus exhibits a remarkable color change and rapid switching rate.
Chemists have long sought sequence-controlled synthetic polymers that mimic nature's biopolymers, but a practical synthetic route that enables absolute control over polymer sequence and structure remains a key challenge. Here, we report an iterative exponential growth plus side-chain functionalization (IEG+) strategy that begins with enantiopure epoxides and facilitates the efficient synthesis of a family of uniform >3 kDa macromolecules of varying sequence and stereoconfiguration that are coupled to produce unimolecular polymers (>6 kDa) with sequences and structures that cannot be obtained using traditional polymerization techniques. Selective side-chain deprotection of three hexadecamers is also demonstrated, which imbues each compound with the ability to dissolve in water. We anticipate that these new macromolecules and the general IEG+ strategy will find broad application as a versatile platform for the scalable synthesis of sequence-controlled polymers.
Multielectron acceptors are essential components for artificial photosynthetic systems that must deliver multiple electrons to catalysts for solar fuels applications. The recently developed boxlike cyclophane incorporating two extended viologen units joined end-to-end by two p-phenylene linkers-namely, ExBox(4+)-has a potential to be integrated into light-driven systems on account of its ability to complex with π-electron-rich guests such as perylene, which has been utilized to great extent in many light-harvesting applications. Photodriven electron transfer to ExBox(4+) has not previously been investigated, however, and so its properties, following photoreduction, are largely unknown. Here, we investigate the structure and energetics of the various accessible oxidation states of ExBox(4+) using a combination of spectroscopy and computation. In particular, we examine photoinitiated electron transfer from perylene bound within ExBox(4+) (ExBox(4+)⊂perylene) using visible and near-infrared femtosecond transient absorption (fsTA) spectroscopy. The structure and conformational relaxation dynamics of ExBox(3+)⊂perylene(+) are observed with femtosecond stimulated Raman spectroscopy (FSRS). From the fsTA and FSRS spectra, we observe that the central p-phenylene spacer in one of the extended viologen units on one side of the cyclophane becomes more coplanar with its neighboring pyridinium units over the first ∼5 ps after photoreduction. When the steady-state structure of chemically generated ExBox(2+) is investigated using Raman spectroscopy, it is found to have the central p-phenylene rings in both of its extended viologen units rotated to be more coplanar with their neighboring pyridinium units, further underscoring the importance of this subunit in the stabilization of the reduced states of ExBox(4+).
The ability of the diradical dicationic cyclobis(paraquat-p-phenylene) (CBPQT2(•+)) ring to form inclusion complexes with 1,1′-dialkyl-4,4′-bipyridinium radical cationic (BIPY•+) guests has been investigated mechanistically and quantitatively. Two BIPY•+ radical cations, methyl viologen (MV•+) and a dibutynyl derivative (V•+), were investigated as guests for the CBPQT2(•+) ring. Both guests form trisradical complexes, namely, CBPQT2(•+)⊂MV•+ and CBPQT2(•+)⊂V•+, respectively. The structural details of the CBPQT2(•+)⊂MV•+ complex, which were ascertained by single-crystal X-ray crystallography, reveal that MV•+ is located inside the cavity of the ring in a centrosymmetric fashion: the 1:1 complexes pack in continuous radical cation stacks. A similar solid-state packing was observed in the case of CBPQT2(•+) by itself. Quantum mechanical calculations agree well with the superstructure revealed by X-ray crystallography for CBPQT2(•+)⊂MV•+ and further suggest an electronic asymmetry in the SOMO caused by radical-pairing interactions. The electronic asymmetry is maintained in solution. The thermodynamic stability of the CBPQT2(•+)⊂MV•+ complex was probed by both isothermal titration calorimetry (ITC) and UV/vis spectroscopy, leading to binding constants of (5.0 ± 0.6) × 104 M–1 and (7.9 ± 5.5) × 104 M–1, respectively. The kinetics of association and dissociation were determined by stopped-flow spectroscopy, yielding a k f and k b of (2.1 ± 0.3) × 106 M–1 s–1 and 250 ± 50 s–1, respectively. The electrochemical mechanistic details were studied by variable scan rate cyclic voltammetry (CV), and the experimental data were compared digitally with simulated data, modeled on the proposed mechanism using the thermodynamic and kinetic parameters obtained from ITC, UV/vis, and stopped-flow spectroscopy. In particular, the electrochemical mechanism of association/dissociation involves a bisradical tetracationic intermediate CBPQT(2+)(•+)⊂V•+ inclusion complex; in the case of the V•+ guest, the rate of disassociation (k b = 10 ± 2 s–1) was slow enough that it could be detected and quantified by variable scan rate CV. All the experimental observations lead to the speculation that the CBPQT(2+)(•+) ring of the bisradical tetracation complex might possess the unique property of being able to recognize both BIPY•+ radical cation and π-electron-rich guests simultaneously. The findings reported herein lay the foundation for future studies where this radical–radical recognition motif is harnessed particularly in the context of mechanically interlocked molecules and increases our fundamental understanding of BIPY•+ radical–radical interactions in solution as well as in the solid-state.
Radically Organic Metals such as manganese are relatively stable over a wide range of oxidation states. In contrast, purely organic compounds are rarely susceptible to incremental addition or removal of electrons without accompanying fragmentation or coupling reactions. Barnes et al. (p. 429 ; see the Perspective by Benniston ) report a catenane (a compound comprising interlocked rings) in which the topological structure stabilizes six different states that successively differ by the presence or absence of one or two electrons in the framework. The hepta-oxidized state proved remarkably resilient to oxygen exposure.
Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor-acceptor interactions to form host-guest complexes with various guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed Ex(n)Boxm(4+) for short, have been prepared by altering a number of variables: (i) n, the number of "horizontal" p-phenylene spacers between adjoining pyridinium units, to modulate the "length" of the cavity; (ii) m, the number of "vertical" p-phenylene spacers, to modulate the "width" of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex(1)Box(4+) (or simply ExBox(4+)) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host-guest complexes allow the development of artificial photosystems. Ex(2)Box(4+) boasts the ability to bind both π-electron-rich and -poor aromatic guests in different binding sites located within the same cavity. ExBox2(4+) forms complexes with C60 in which discrete arrays of aligned fullerenes result in single cocrystals, leading to improved material conductivities. When the substitution pattern of the Ex(n)Box(4+) series is changed to 1,3,5-trisubstituted benzenoid cores, the hexacationic cagelike compound, termed ExCage(6+), exhibits different kinetics of complexation with guests of varying sizes-a veritable playground for physical organic chemists. The organization of functionality with respect to structure becomes valuable as the number of analogues continues to grow. With each of these minor structural modifications, a wealth of properties emerge, begging the question as to what discoveries await and what properties will be realized with the continued exploration of this area of supramolecular chemistry based on a unique class of receptor molecules.
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