ABSTRACT
In reticular chemistry, molecular building blocks are designed to create crystalline open frameworks. A key principle of reticular chemistry is that the most symmetrical networks are the likely outcomes of reactions, particularly when highly symmetrical building blocks are involved. The strategy of synthesizing low-dimensional networks aims to reduce explicitly the symmetry of the molecular building blocks. Here we report the spontaneous formation of hydrogen-bonded fibrous structures from trigonal prismatic building blocks, which were designed to form three-dimensional crystalline networks on account of their highly symmetrical structures. Utilizing different microscopic and spectroscopic techniques, we identify the structures at the early stages of the assembly process in order to and understand the growth mechanism. The symmetrical molecular building blocks are incorporated preferentially in the longitudinal direction, giving rise to anisotropic hydrogen-bonded porous organic nanotubes. Entropy-driven anisotropic growth provides micrometer-scale unidirectional nanotubes with high porosity. By combining experimental evidence and theoretical modeling, we have obtained a deep understanding of the nucleation and growth processes. Our findings offer fundamental insight into the molecular design of tubular structures. The nanotubes evolve further in the transverse directions to provide extended higher-order fibrous structures [nano- and microfibers], ultimately leading to large-scale interconnected hydrogen-bonded fiber-like structures with twists and turns. Our work provides fundamental understanding and paves the way for innovative molecular designs in low-dimensional networks.
ABSTRACT
Enzymes are natural catalysts for a wide range of metabolic chemical transformations, including selective hydrolysis, oxidation, and phosphorylation. Herein, we demonstrate a strategy for the encapsulation of enzymes within a highly stable zirconium-based metal-organic framework. UiO-66-F4 was synthesized under mild conditions using an enzyme-compatible amino acid modulator, serine, at a modest temperature in an aqueous solution. Enzyme@UiO-66-F4 biocomposites were then formed by an in situ encapsulation route in which UiO-66-F4 grows around the enzymes and, consequently, provides protection for the enzymes. A range of enzymes, namely, lysozyme, horseradish peroxidase, and amano lipase, were successfully encapsulated within UiO-66-F4. We further demonstrate that the resulting biocomposites are stable under conditions that could denature many enzymes. Horseradish peroxidase encapsulated within UiO-66-F4 maintained its biological activity even after being treated with the proteolytic enzyme pepsin and heated at 60 °C. This strategy expands the toolbox of potential metal-organic frameworks with different topologies or functionalities that can be used as enzyme encapsulation hosts. We also demonstrate that this versatile process of in situ encapsulation of enzymes under mild conditions (i.e., submerged in water and at a modest temperature) can be generalized to encapsulate enzymes of various sizes within UiO-66-F4 while protecting them from harsh conditions (i.e., high temperatures, contact with denaturants or organic solvents).
Subject(s)
Metal-Organic Frameworks , Organometallic Compounds , Phthalic Acids , Metal-Organic Frameworks/chemistry , Zirconium/chemistry , Biomimetics , Organometallic Compounds/chemistry , Horseradish PeroxidaseABSTRACT
Dioxobimanes, colloquially known as bimanes, are a well-established family of N-heterobicyclic compounds that share a characteristic core structure, 1,5-diazabicyclo[3.3.0]octadienedione, bearing two endocyclic carbonyl groups. By sequentially thionating these carbonyls in the syn and anti isomers of the known (Me,Me)dioxobimane, we were able to synthesize a series of thioxobimanes, representing the first heavy-chalcogenide bimane variants. These new compounds were extensively characterized spectroscopically and crystallographically, and their aromaticity was probed computationally. Their potential role as ligands for transition metals was demonstrated by synthesizing a representative gold(I)-thioxobimane complex.
ABSTRACT
Polar and polarizable π-conjugated organic molecules containing push-pull chromophores have been investigated extensively in the past. Identifying unique backbones and building blocks for fluorescent dyes is a timely exercise. Here, we report the synthesis and characterization of a series of fluorescent dyes containing quadrupolar A-D-A constitutions (where A = acceptor and D = donor), which exhibit fluorescence emission at a variety of different wavelengths. We have investigated the effects of different electron-withdrawing groups, located at both termini of a para-terphenylene backbone, by steady-state UV/vis and fluorescence spectroscopy. Pyridine and substituted pyridinium units are also introduced during the construction of the quadrupolar backbones. Depending on the quadrupolarity, fluorescence emission wavelengths cover from 380 to 557 nm. Time-resolved absorption and emission spectroscopy reveal that the photophysical properties of those quadrupolar dyes result from intramolecular charge transfer. One of the dyes we have investigated is a symmetrical box-like tetracationic cyclophane. Its water-soluble tetrachloride, which is non-cytotoxic to cells up to a loading concentration of 1 µM, has been employed in live-cell imaging. When taken up by cells, the tetrachloride emits a green fluorescence emission without any hint of photobleaching or disruption of normal cell behavior. We envision that our design strategy of modifying molecules through the functionalization of the quadrupolar building blocks as chromophores will lead to future generations of fluorescent dyes in which these A-D-A constitutional fragments are incorporated into more complex molecules and polymers for broader photophysical and biological applications.
Subject(s)
Fluorescent Dyes , Pyridines , Alcohols , Fluorescent Dyes/chemistry , Polymers , WaterABSTRACT
With the serendipitous discovery of crown ethers by Pedersen more than half a century ago and the subsequent introduction of host-guest chemistry and supramolecular chemistry by Cram and Lehn, respectively, followed by the design and synthesis of wholly synthetic cyclophanes-in particular, fluorescent cyclophanes, having rich structural characteristics and functions-have been the focus of considerable research activity during the past few decades. Cyclophanes with remarkable emissive properties have been investigated continuously over the years and employed in numerous applications across the field of science and technology. In this Review, we feature the recent developments in the chemistry of fluorescent cyclophanes, along with their design and synthesis. Their host-guest chemistry and applications related to their structure and properties are highlighted.
ABSTRACT
The phenomenon of photon upconversion, in which a system absorbs two or more photons of lower energy and emits a photon of higher energy, has been used in numerous applications, including non-destructive bioimaging, deep-penetrating photodynamic therapy, catalysis, and photovoltaic devices. To date, photon upconversion has been observed typically in inorganic nanocrystals, nanoparticles, metal-organic frameworks, supramolecular assemblies, and organic dyads. Herein, we demonstrate a new strategy for harnessing photon upconversion-supramolecular upconversion-based on host-guest chemistry. We have identified a box-like fluorescent tetracationic host incorporating a thiazolothiazole emitter, which can accommodate a guest-sensitizer, 5,15-diphenylporphyrin, inside its cavity, and demonstrated that the host-guest inclusion complex displays triplet-fusion upconversion when the guest is excited with low-energy light. The strategy of supramolecular upconversion has been employed successfully in two other host-guest complexes-with hosts comprised of anthracene emitters and a 5,15-diphenylporphyrin guest-corroborating the fact that this strategy is a general one and can be applied to the design of a new family of host-guest complexes for photon upconversion. More importantly, supramolecular upconversion is accessible in solution under dilute conditions (µM) compared to most of the existing approaches that require significantly higher concentrations (mM) of emitters and/or sensitizers. Transient absorption spectroscopy and density functional theory have been employed in order to confirm a triplet-fusion upconversion mechanism. Host-guest complexation-mediated supramolecular photon upconversion eliminates multiple issues in the existing systems related to high working concentrations, high incident laser power, and low optical penetration depths.
ABSTRACT
INTRODUCTION: With the advancement in imaging technology, 3D dental computed tomography plays a very significant role in orthodontic treatment and diagnosis. AIM: To evaluate dental crowding in relation to the mesiodistal crown widths and arch dimensions and also to determine the differences of dental crowding among males and females, in Southern Indian population. MATERIALS AND METHODS: A total of 132 subjects were divided into two groups: crowded and non-crowded, each comprising 66 subjects (33 males and 33 females), aged between 15 and 35 years, who were referred for computed tomography scan of brain to the radiology department, were selected. During the scan both the jaws were included in the image. The 2D images were converted to 3D images using volume rendering software. By using measurement tool, individual and collective mesiodistal crown widths of canine, first and second premolar and first molar and arch perimeter of both the maxillary and mandibular jaws were measured. RESULTS: When both the gender were considered, the mesiodistal crown widths and arch perimeter were statistically significant for dental crowding in both mandibular jaw (p-value=0.001 for both mesiodistal crown width and arch perimeter) and maxillary jaw (p-value=0.016 for mesiodistal crown width and 0.002 for arch perimeter). However, when analysed separately, in males the mesiodistal crown widths and arch perimeter were statistically significant for dental crowding in both mandibular jaw (p-value=0.001 for mesiodistal crown width and 0.002 for arch perimeter) and maxillary jaw (p-value=0.002 for mesiodistal crown width and 0.001 for arch perimeter) but in females it was not statistically significant in any jaw (p-value=0.7 for mesiodistal crown width and 0.06 for arch perimeter in mandibular jaw and p-value=0.2 for mesiodistal crown width and 0.9 for arch perimeter for maxillary jaw). The crowded group had larger tooth size and smaller arch perimeter. CONCLUSION: This study concluded that in males, both the factors i.e., mesiodistal crown width and arch dimensions contributed to dental crowding and the crowded dentition had larger mesiodistal tooth size and smaller arch dimensions; whereas, in females both the factors were not responsible for crowding in Southern Indian population.
ABSTRACT
A cationic Pd(ii) complex containing syn-(Me,Me)bimane as a ligand was prepared and fully characterized. This complex represents the first well-defined case of a bimane scaffold coordinated to a metal center. The strongly-fluorescent syn-bimane chelates the Pd(ii) center via its carbonyl oxygen atoms, affording a non-fluorescent complex. The crystal structure of this complex shows that the coordinated bimane departs from planarity, with its bicyclic framework bent about the N-N bond. Spectroscopic evidence demonstrates that bimane coordination is reversible in solution.