Chlorination of microcystin-LR in natural water: Kinetics, transformation products, and genotoxicity.

Microcystin-LR (MC-LR), a type of cyanotoxin commonly found in natural water bodies (sources of drinking water), poses a threat to human health due to its high toxicity. It is essential to successfully remove this cyanotoxin from drinking water sources. In this study, chlorine was used to oxidize MC-LR in Milli-Q water (MQ) (control test) and natural water collected from Lake Longhu (LLW) as a drinking water source. The removal efficiency, proposed transformation pathways, and genotoxicity were investigated. In the chlorine dose range investigated (4.0 mg L-1 - 8.0 mg L-1), the apparent second-order rate constants for MC-LR chlorination varied from 21.3 M-1s-1 to 31.9 M-1s-1 in MQ, higher than that in LLW (9.06 M-1s-1 to 17.7 M-1s-1) due to a faster chlorine decay attributed to the water matrix (e.g., natural organic matter) of LLW. Eleven transformation products (TPs) of MC-LR were identified in the two waters. The conjugated diene moieties and benzene ring of Adda moiety (3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid), and the double bond of Mdha moiety (N-methyldehydroalanine) were the major susceptible reaction sites. Attacking unsaturated bonds by hydroxyl and chlorine radicals to generate monochloro-hydroxy-MC-LR was the primary initial transformation pathway, followed by nucleophilic substitution, dehydration, and cleavage in MC-LR. Chlorine substitution on the benzene ring was also observed. Based on the bacterial reverse-mutation assay (Ames assay), TPs in treated natural water did not induce genotoxicity/mutagenicity. These findings shed light on the role of chlorination in controlling the risk of cyanotoxins in drinking water treatment plants.

Large π-Extended and Curved Carbon Nanorings as Carbon Nanotube Segments.

ConspectusDesigning and synthesizing topologically unique molecules is a long-term challenge for synthetic chemists. Classical polycyclic aromatic hydrocarbons (PAHs) are a large group of π-conjugated planar organic compounds with rich photophysical and electronic properties, while nonplanar/curved PAHs have different molecular orbital arrangements and demonstrate unique properties. The chemistry of curved aromatic molecules has been of significant interest to explore the relationship between π conjugation and molecular geometry, which offers an attractive combination of fundamental problems, potential applications, and aesthetic appeal. Remarkable advances have been made in the last few decades during the discovery of novel curved aromatic molecules, including corannulenes, fullerenes, and carbon nanotubes (CNTs). Especially, there has been increasing interest in making single-chirality CNTs and their curved molecular components (known as finite segments of CNTs) with a fixed geometry. The most representative examples of such organic molecules are cycloparaphenylenes (CPPs) and related carbon nanorings, which possess cylindrical topologies and nanoscale conjugated segments similar to CNTs. CPPs, as the shortest cross-section and the simplest structure of armchair CNTs, have been synthetically accessible since 2008. Recent years have witnessed breakthroughs and rapid development in the synthesis of CPP-based nanorings as well as their derived molecules. In these molecules, the distortion from aromatic planarity can induce radially oriented π systems and further affect their electronic, optical, self-assembly, and charge-transport characteristics. These unique and interesting carbon nanorings are potentially useful in a variety of optoelectronic and biomedical materials. It is well-known that extension of the π-conjugated system facilitates the delocalization of π electrons and the redistribution of electronic clouds, leading to rich diversification of physical properties in the fields of electronics, optics, and supramolecular chemistry. Therefore, the precise design and controllable synthesis of carbon nanorings with large π conjugation will promote important advances in synthetic chemistry. To date, a number of π-extended carbon nanorings have been reported, and they exhibit novel physicochemical properties resulting from their fascinating topologies and structures. However, challenges still remain in the synthesis of π-extended carbon nanorings and their structural analogues and exploration of their unique properties.In this Account, we give a brief overview of our efforts to synthesize large π-extended carbon nanorings using different strategies and explore their novel applications. In 2013 we started our research on the synthesis of carbon nanorings with large π-conjugated structures. This research project has led to (i) the successful preparation of a series of carbon nanorings with inserted PAHs, especially with various nanographenes inserted, such as hexa-peri-hexabenzocoronene; (ii) the design and synthesis of a series of carbon nanorings consisting solely of PAHs; and (iii) the initial synthesis of π-extended carbon-nanoring-based polymers as the long polymeric segments of CNTs, in which macrocyclic CPPs as the basic repeating blocks were covalently coupled together. Herein we describe in detail how these challenging π-extended carbon nanorings were synthesized, and their interesting physical properties are discussed.

Tuning the (Chir)Optical Properties and Squeezing out the Inherent Chirality in Polyphenylene-Locked Helical Carbon Nanorings.

Distorting linear polyaromatic hydrocarbons (PAHs) out of planarity affects their physical properties and breaks their symmetry to induce inherent chirality. However, the chirality cannot be achieved in large distorted PAHs-based macrocycles due to a low racemization barrier for isomerization. Herein, we report the precise synthesis and tuning size-dependent (chir)optical properties of a new class of chiral PAHs-containing conjugated macrocycles (cyclo[n]paraphenylene-2,6-anthrylene, [n]CPPAn2,6 ; n=6-8). Their inherent chiralities were squeezed out in small anthrylene-based macrocycles. Efficient resolutions for chiral enantiomers with (P)/(M)-helicity of small [6-7]CPPAns were achieved by HPLC. Interestingly, these macrocycles showed enriched size-dependent physical, chiral, and (chir)optical properties. Theoretical calculations indicate that these macrocycles have high strain energy (Estrain =60.8 to 73.4 kcal/mol) and very small Egap (∼3.0 eV). Notably, these enantiomers showed strong chiroptical properties and dissymmetry factors (|gabs | and |glum |∼0.01 for an enantiomer of [6]CPPAn2,6 ), which can give them potential applications in optically active materials.

Synthesis and Photophysical Properties of [3]Cyclo-1,8-pyrenes via [4 + 2] Cycloaddition Reaction.

Herein, we report the synthesis, characterization, and photophysical properties of the crown-like structure of [3]cyclo-1,8-pyrenes (compounds 9 and 10). Planar pyrenyl arylene-ethynylene macrocycles are used as the precursors to synthesize these pyrene-based cycloarenes by [4 + 2] cycloaddition reaction with good yields. These molecules are confirmed by nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. The structure of 9 was unambiguously determined by single-crystal X-ray diffraction. Their photophysical properties are investigated by steady-state absorption, fluorescence, and time-resolved fluorescence spectroscopies, combined with theoretical calculations.

A Highly Strained All-Phenylene Conjoined Bismacrocycle.

Herein, we report the precise synthesis of a 3D highly strained all-phenylene bismacrocycle, termed conjoined (1,4)[10]cycloparaphenylenophane (SCPP[10]). This structure consists of a twisted benzene ring which is bridged twice by phenylene units anchored in two para-positions. The conjoined structure of SCPP[10] was confirmed in real space at the atomic scale by scanning tunneling microscopy. Theoretical calculations indicate that this bismacrocycle has a very high strain energy of 110.59 kcal mol-1 and the largest interphenylene torsion angle of 46.07° caused by multiple repulsive interactions. Furthermore, a 1:2 host-guest complex of SCPP[10] and [6,6]-phenyl-C61 -butyric acid methyl ester was investigated, which represents the first peanut-shaped 1:2 host-guest complex based on bismacrocycles.

A Long π-Conjugated Poly(para-Phenylene)-Based Polymeric Segment of Single-Walled Carbon Nanotubes.

Conjugated polymers have attracted much attention for many years and have applications in various organic devices. Carbon nanotubes can be considered as all-carbon tube-shaped conjugated polymers containing only sp2-bonded atoms, which play an important role in nanotechnology and nanoelectronics. So far, no study has reported the realization of long π-conjugated polymers as diameter-specified carbon nanotube segments. Herein, we report the first synthesis of a π-conjugated polymeric segment (PS1) of armchair single-walled carbon nanotubes (SWCNTs). PS1 is achieved by a rationally designed synthesis of a bifunctionalized cyclo-para-phenylene monomer, followed by inserting these ring-shaped units into the conjugated poly(para-phenylene) backbone. PS1 was fully characterized by gel permeation chromatography (GPC) combined with NMR, FTIR, and Raman spectra. Possessing unique structural and physical properties, this long π-extended polymer PS1 can provide new insight for the development of bottom-up syntheses of uniform carbon nanotube segments and potential applications in electron- and hole-transport devices.

Ammonium hydroxide modulated synthesis of high-quality fluorescent carbon dots for white LEDs with excellent color rendering properties.

A novel type of aqueous fluorescent carbon dot (CD) was synthesized using citric acid as the only carbon source via an ammonium hydroxide modulated method, providing a blue color gamut. The amino group is considered to be the key factor in the high fluorescence of CDs and a model is established to investigate the mechanism of fluorescence. In addition, white light-emitting diodes (WLEDs) are fabricated by utilizing the prepared CDs and rare earth luminescent materials (SrSi2O2N2:Eu and Sr2Si5N8:Eu) as color conversion layers and UV-LED chips as the excitation light source. The WLEDs produce bright white light with attractive color rendering properties including a color rendering index of up to 95.1, a CIE coordinate of (0.33, 0.37), and a T c of 5447 K under a 100 mA driven current, indicating that the CDs are promising in the field of optoelectronic devices.

Synthesis and Physical Properties of a Perylene Diimide-Embedded Chiral Conjugated Macrocycle.

Herein, we report the facile synthesis and properties of a chiral perylene diimide (PDI)-embedded conjugated macrocycle (cyclo[6]paraphenylene-1,7-perylene diimide, [6]CPP-PDI1,7) by Pd-catalyzed Suzuki coupling and a subsequent reductive aromatization reaction in two steps. The PDI-embedded conjugated macrocycle showed a significant redshift (>110 nm for absorption) compared to the PDI molecule. Moreover, efficient resolution of chiral enantiomers with (P)/(M)-[6]CPP-PDI1,7 was achieved by high-performance liquid chromatography, and their chiral properties were investigated by circular dichroism spectroscopy. The realization of [6]CPP-PDI1,7 expands the scope of the precise synthesis of PDI-embedded chiral conjugated macrocycles and explores its unique physical properties.

A metal-free photoactive nitrogen-doped carbon nanosolenoid with broad absorption in visible region for efficient photocatalysis.

Riemann surfaces inspired chemists to design and synthesize such multidimensional curved carbon architectures. It has been predicted that carbon nanosolenoid materials with Riemann surfaces have unique structures and novel physical properties. Here we report the first synthesis of a nitrogen-doped carbon nanosolenoid (N-CNS) using bottom-up approach with a well-defined structure. N-CNS was obtained by a rational Suzuki polymerization, followed by oxidative cyclodehydrogenation. The successful synthesis of N-CNS was fully characterized by GPC, FTIR, solid-state 13C NMR and Raman techniques. The intrinsic single-strand molecular structures of N-CNS helices can be clearly resolved using low-dose integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM) technique. Possessing unique structural and physical properties, this long π-extended polymer N-CNS can provide new insight towards bottom-up syntheses of curved nanoribbons and potential applications as a metal-free photocatalyst for visible-light-driven H2 evolution and highly efficient photocatalyst for photoredox organic transformations.

Highly efficient charge transport across carbon nanobelts.

Carbon nanobelts (CNBs) are a new form of nanocarbon that has promising applications in optoelectronics due to their unique belt-shaped π-conjugated systems. Recent synthetic breakthrough has led to the access to various CNBs, but their optoelectronic properties have not been explored yet. In this work, we study the electronic transport performance of a series of CNBs by incorporating them into molecular devices using the scanning tunneling microscope break junction technique. We show that, by tuning the bridging groups between the adjacent benzenes in the CNBs, we can achieve remarkably high conductance close to 0.1 G0, nearly one order of magnitude higher than their nanoring counterpart cycloparaphenylene. Density functional theory-based calculations further elucidate the crucial role of the structural distortion played in facilitating the unique radial π-electron delocalization and charge transport across the belt-shaped carbon skeletons. These results develop a basic understanding of electronic transport properties of CNBs and lay the foundation for further exploration of CNB-based optoelectronic applications.

Synthesis of a magnetic π-extended carbon nanosolenoid with Riemann surfaces.

Riemann surfaces are deformed versions of the complex plane in mathematics. Locally they look like patches of the complex plane, but globally, the topology may deviate from a plane. Nanostructured graphitic carbon materials resembling a Riemann surface with helicoid topology are predicted to have interesting electronic and photonic properties. However, fabrication of such processable and large π-extended nanographene systems has remained a major challenge. Here, we report a bottom-up synthesis of a metal-free carbon nanosolenoid (CNS) material with a low optical bandgap of 1.97 eV. The synthesis procedure is rapid and possible on the gram scale. The helical molecular structure of CNS can be observed by direct low-dose high-resolution imaging, using integrated differential phase contrast scanning transmission electron microscopy. Magnetic susceptibility measurements show paramagnetism with a high spin density for CNS. Such a π-conjugated CNS allows for the detailed study of its physical properties and may form the base of the development of electronic and spintronic devices containing CNS species.

Synthesis and Physical Properties of a Phenanthrene-Based [6,6] Hollow Bilayer Cylindrical Nanoring.

Herein, we report the synthesis and properties of a [6,6] hollow bilayer cylindrical nanoring (HBCNR) from a planar macrocycle via a Diels-Alder and Yamamoto coupling reaction. The fluorescence quantum yield of HBCNR was determined to be ΦF = 52%, which is four times higher than its precursor. In addition, its hollow nanoring configuration was also simulated by theoretical studies, and the tension energy was estimated to be 47.1 kcal/mol.

Precise membrane separation of nanoparticles using a microporous polymer containing radially π-conjugated molecular carbocycles.

Herein, we report the synthesis of a novel porous polymer, PS2, containing radially π-conjugated carbocycles and a linear phenylene backbone. The PS2-based membrane has a distinct small size cutoff (ca. 2.6 nm) and a major size at ∼1.5 nm for the size-selective separation of nanoparticles.

Synthesis and properties of a nanographene-embedded conjugated macrocyclic nanoring via the Scholl reaction.

Direct π-extension by the Scholl reaction for solution-based growth of armchair edges in curved macrocyclic hydrocarbon nanostructures is a great challenge. To date, several attempts at direct π-extension of small highly strained macrocycles have failed. Herein, we report a fixed two-bond approach for direct functionalization of small strained macrocyclic nanorings. The reaction occurs selectively to produce large π-extended molecular crowns with high yields. The design of these precursors features two peripheral C-C bonds that are readily incorporated into the extended aromatic moiety to overcome strain-induced side reactions, such as 1,2-phenyl shift. The crown-shaped macrocycle 10 showed a significant redshift (∼100 nm for absorption) compared with its precursor. This synthesis strategy could pave the way towards the π-extension of strained conjugated macrocycles and their potential applications in electron-transport devices.

A supramolecular polymeric heterojunction composed of an all-carbon conjugated polymer and fullerenes.

Herein, we design and synthesize a novel all-carbon supramolecular polymer host (SPh) containing conjugated macrocycles interconnected by a linear poly(para-phenylene) backbone. Applying the supramolecular host and fullerene C60 as the guest, we successfully construct a supramolecular polymeric heterojunction (SPh⊃C60). This carbon structure offers a means to explore the convex-concave π-π interactions between SPh and C60. The produced SPh was characterized by gel permeation chromatography, mass spectrometry, FTIR, Raman spectroscopy, and other spectroscopies. The polymeric segment can be directly viewed using a scanning tunneling microscope. Femtosecond transient absorption and fluorescence up-conversion measurements revealed femtosecond (≪300 fs) electron transfer from photoexcited SPh to C60, followed by nanosecond charge recombination to produce the C60 triplet excited state. The potential applications of SPh⊃C60 in electron- and hole-transport devices were also investigated, revealing that C60 incorporation enhances the charge transport properties of SPh. These results expand the scope of the synthesis and application of supramolecular polymeric heterojunctions.

The Supramolecular Chemistry of Cycloparaphenylenes and Their Analogs.

Cycloparaphenylenes (CPPs) and their analogs have recently attracted much attention due to their aesthetical structures and optoelectronic properties with radial π-conjugation systems. The past 10 years have witnessed a remarkable advancement in CPPs research, from synthetic methodology to optoelectronic investigations. In this present minireview, we highlight the supramolecular chemistry of CPPs and their analogs, mainly focusing on the size-selective encapsulation of fullerenes, endohedral metallofullerenes, and small molecules by these hoop-shaped macrocycles. We will also discuss the assembly of molecular bearings using some belt-persistent tubular cycloarylene molecules and fullerenes, photoinduced electron transfer properties in supramolecular systems containing carbon nanohoop hosts and fullerene guests, as well as the shape recognition properties for structure self-sorting by using dumbbell-shaped dimer of [60]fullerene ligand. Besides, the supramolecular complexes with guest molecules other than fullerenes, such as CPPs themselves, iodine, pyridinium cations, and bowl-shaped corannulene, are also discussed.

From Planar Macrocycle to Cylindrical Molecule: Synthesis and Properties of a Phenanthrene-Based Coronal Nanohoop as a Segment of [6,6]Carbon Nanotube.

Herein, we explore phenanthrene as the building block to synthesize a hoop-shaped [6,6]carbon nanotube segment from a planar macocycle via a Diels-Alder reaction. The phenanthrene-based coronal nanohoop 7 was fully characterized by HR-MS, NMR, and other spectroscopies. In addition, its photophysical properties and the supramolecular interactions between 7 and fullerene C60 were investigated. This present work suggests an easily accessible Diels-Alder reaction strategy to synthesize cylindrical nanohoops.