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Life is homochiral and homochirality is a fundamental feature of living systems on Earth. While the exact mechanism that led to homochirality is still not fully understood, any realistic scenario on the origins of life needs to address the emergence of homochirality. In order to impose and maintain chirality in a prebiotic network, an environmental factor functioning as a chiral agent is demanded. Magnetized surfaces are prebiotically plausible chiral agents, shown to be effective in enantioseparation of ribose-aminooxazoline (RAO), a ribonucleic acid (RNA) precursor, due to the chiral-induced spin selectivity (CISS) effect. As such, mechanisms for breaking the magnetic symmetry of magnetic minerals are of the utmost importance. Here we report the avalanche magnetization of magnetite $(Fe_{3}O_{4})$ by the crystallization of enantiopure RAO. The observed breaking of the magnetic symmetry is induced by the chiral molecules due to the CISS effect and spreads out across the magnetic surface like an avalanche, providing a way to uniformly magnetize a magnetic surface without fully covering it. Considered together with our previous results on enantioseparation by crystallization on a magnetic surface, chirality-induced avalanche magnetization paves the way for a cooperative feedback between chiral molecules and magnetic surfaces. With this feedback, a weak natural bias in the net magnetization can be amplified and spin-selective processes can be accommodated on magnetic minerals on a persistent basis., 19 pages, 6 figures

Here we describe the self-assembly of an achiral molecule into macroscopic helicity as well as the emergent chirality selective spin filtering effect. It was found that benzene-1,3,5-tricarboxamide (BTA) motif with an aminopyridine group in each arm could coordinate with Ag(I) and self-assemble into nanospheres. Upon sonication symmetry breaking occurred and the nanospheres transfer into helical nanofibers with strong CD signals. Although the sign of the CD signals appeared randomly, it could be controlled by using the as-made chiral assemblies as a seed. Furthermore, it was found that the charge transport of the helical nanofibers was highly selective with a spin-polarization transport of up to 45% although the chiral nanofibers are composed exclusively from achiral building blocks. The work demonstrated a new example of the symmetry breaking under sonication and the chirality selective spin filtering effect.

The oxygen reduction reaction (ORR) is of high importance, among others because of its role in cellular respiration and in the operation of fuel cells. Recently, a possible relation between respiration and general anesthesia has been found. This work aims to explore whether anesthesia related gases affect the ORR. In ORR, oxygen which is in its triplet ground state is reduced to form products that are all in the singlet state. While this process is “in principle” forbidden because of spin conservation, it is known that if the electrons transferred in the ORR are spin polarized, the reaction occurs efficiently. Here we show, in electrochemical experiments, that the efficiency of the oxygen reduction is reduced by the presence of general anesthetics in solution. We suggest that a spin-orbit coupling to the anesthetics depolarizes the spins. This causes both a reduction in reaction efficiency and a change in the reaction products. The findings may point to a possible relation between ORR efficiency and anesthetic action.TOC

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here, we show that the electron transfer efficiency from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin–orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral-induced spin selectivity effect.

Applying magnetic substrates, magnetized perpendicular to the surface, we were able to crystallize from racemic solution pure conglomerates of several molecules. The resolution is based on the spin...

Among the enticing issues of chiral origins are: how chirality is born from the initial achiral units and the mechanisms for the transfer of chiral information. In this work, by combining a physical vortex and chiral seeds, a general process is revealed to generate chiral supramolecular polymers from achiral C

Enormous attention has been paid to upconverted circularly polarized luminescence (UC-CPL). However, so far, chiral species are still needed in UC-CPL materials, either through the covalent or noncovalent bond. Here, we report a general supramolecular coassembly approach for the fabrication of UC-CPL systems from completely achiral components. We have found that an achiral C3-symmetric molecule could form a chiral nanohelix through symmetry breaking, which could serve as a general helical platform to endow achiral guests with induced chirality and CPL activity. Two different photon upconversion systems, namely, triplet-triplet annihilation photon upconversion (TTA-UC) donor/acceptor pairs and inorganic lanthanide upconversion nanoparticles (UCNPs), are selected. When these two systems coassembled with the chiral nanohelix made from an achiral C3-symmetric molecule, hybrid nanohelix structures formed and UC-CPL activity was induced. Through such an approach, we demonstrated that the fabrication of the UC-CPL materials does not require any chiral molecules. Moreover, we have shown that the polarization of UC-CPL can be tuned by the helicity of the nanohelix, which could be controlled through the seeded vortex. Our work provides a general approach for designing tunable UC-CPL materials from completely achiral motifs, which largely expands the research scope of the CPL materials.

Consecutive boosted circularly polarized luminescence (CPL) with controlled handedness has been demonstrated in a supramolecular assembly from a completely achiral molecule. It is found that achira...

Although chirality has been recognized as an essential entity for life, it still remains a big mystery how the homochirality in nature emerged in essential biomolecules. Certain achiral motifs are known to assemble into chiral nanostructures. In rare cases, their absolute geometries are enantiomerically biased by mirror symmetry breaking. Here we report the first example of asymmetric catalysis by using a mirror symmetry-broken helical nanoribbon as the ligand. We obtain this helical nanoribbon from a benzoic acid appended achiral benzene-1,3,5-tricarboxamide by its helical supramolecular assembly and employ it for the Cu2+-catalyzed Diels–Alder reaction. By thorough optimization of the reaction (conversion: > 99%, turnover number: ~90), the enantiomeric excess eventually reaches 46% (major/minor enantiomers = 73/27). We also confirm that the helical nanoribbon indeed carries helically twisted binding sites for Cu2+. Our achievement may provide the fundamental breakthrough for producing optically active molecules from a mixture of totally achiral motifs., If asymmetric catalysts were available by mirror symmetry breaking, an important insight may be given to how the biomolecular homochirality emerged in nature. Here, the authors report the first example of asymmetric catalysis by employing mirror symmetry-broken helical nanoribbons as the ligand.

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here we show that electron transfer from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral induced spin selectivity effect.

Research on chiral selection and recognition not only is of fundamental importance in resolving the origin of biological homochirality, but also is instructive in the fabrication of controlled molecular organization in supramolecular systems to modulate their chirality-related functional properties. Here we report an enantioselective assembly process between a chiral energy donor and two enantiomeric energy acceptors, which further results in chirality-controlled energy transfer and enantioselective triplet-triplet annihilation upconversion (TTA-UC). It is found that the chiral energy donor Pd(II) octaethylporphyrin derivative PdOEP-LG12 (RD) can selectively coassemble with the chiral energy acceptor LGAn (RA) with the same chiral scaffold but tends to form segregation with the energy acceptor DGAn (SA) with the opposite chiral scaffold in a thermodynamic equilibrium state. Thus, the coassembly of RA/RD shows more effective triplet-triplet energy transfer (TTET) and stronger upconverted luminescence and upconverted circularly polarized luminescence in comparison to the segregation of SA/RD. The establishment of such an enantioselective TTA-UC system highlights the applications of chirality-regulated triplet fusion in optoelectronic materials.

The steady-state charge and spin transfer yields were measured for three different Ru-modified azurin derivatives in protein films on silver electrodes. While the charge-transfer yields exhibit weak temperature dependences, consistent with operation of a near activation-less mechanism, the spin selectivity of the electron transfer improves as temperature increases. This enhancement of spin selectivity with temperature is explained by a vibrationally induced spin exchange interaction between the Cu(II) and its chiral ligands. These results indicate that distinct mechanisms control charge and spin transfer within proteins. As with electron charge transfer, proteins deliver polarized electron spins with a yield that depends on the protein’s structure. This finding suggests a new role for protein structure in biochemical redox processes.

Achieving a higher dissymmetry factor is a crucial issue in developing circularly polarized luminescence (CPL) materials. Here, by tailoring the solvent composition and the morphology of the same chiral emissive small molecules (R- or S-SPAn), circularly polarized emission with a boosted dissymmetry factor (two orders) was realized. It was found that by regulating the water fraction in the mixed THF/H2O, we were able to achieve kinetic control over association of chiral emissive R- or S-SPAn into various nanostructures with 0D nanospheres, 2D nanoflakes and 3D stacked nanoflakes. These nanostructures are all CPL active. Remarkably, the dissymmetry factors of the nanostructures were significantly enhanced compared to those of the molecules and further boosted in different morphologies, from ∼10−4 (0D nanospheres) to 10−3 (2D flake) to ∼10−2 (3D nanoflakes). The enlarged glum value could be assigned to a good packing induced strong luminescence of an excimer. This strategy provides an efficient way to fabricate higher dissymmetry factor CPL organic nanomaterials by only changing the supramolecular architectures while using the same chiral small molecules.

Enantiomeric diaminocyclohexane was found to trigger the self-assembly of achiral monomers into chiral supramolecular assemblies with strong circularly polarized luminescence.

By using a vortex mixing-accompanied self-assembly strategy, homochiral entities with controlled handedness were obtained from exclusively achiral molecules., Achieving homochirality is challenging both at the molecular and the supramolecular levels. While the origin of molecular homochirality still remains mysterious, the fabrication of homochiral assemblies from achiral molecules has attracted considerable interest since it provides many clues to understand the origin of molecular chirality. Here, by using a vortex mixing-accompanied self-assembly strategy, we obtained near-unity homochiral entities with controlled handedness from supramolecular gels that consist of exclusively achiral molecules without any chiral additives. The common supramolecular gelation process via heating and cooling of the achiral molecules only resulted in racemic gels. However, if vortex mixing is applied during the self-assembly, near-unity homochiral assemblies with uncontrolled handedness were obtained. Vortex mixing during the nucleation stage was found to be crucial in this case. On the other hand, if a small amount of the above vortex mixing produced assemblies was added as chiral seeds into the racemic gels, the racemic gels turned into near-unity homochiral suspensions with controlled handedness via a ripening process. Our studies provide an intriguing approach for achieving homochiral supramolecular assemblies from achiral molecules.

Supramolecular gels are currently an important class of soft materials that are attracting great interest. The gelation process has been proven to be a powerful approach for the construction of diverse and uniform architectures. Generally, these architectures are on the nanoscale and hierarchically self-assembled from small molecules. Nanoarchitectonics tries to bridge the gap between molecules and nanostructures, while supramolecular gelation provides a good platform to realize such a goal. While the design of the gelator molecules and the function of the gel are important topics, here, we focus on how small molecules can be fabricated into nanostructures through gelation, which is in fact the connection between the microstructures to the macroscopic functions. We showed meritorious examples of typical architectures constructed through the supramolecular gelation process. Then some examples showing the transformation or switching between different nanostructures are presented, which reflected the unique responsiveness of the gel system. Through these two key parts, we hope to provide useful insights into the design and control of functional nanoarchitectures via supramolecular gelation.

The origin of homochirality in life is a fundamental mystery. Symmetry breaking and subsequent amplification of chiral bias are regarded as one of the underlying mechanisms. However, the selection and control of initial chiral bias in a spontaneous mirror symmetry breaking process remains a great challenge. Here we show experimental evidences that laminar chiral microvortices generated within asymmetric microchambers can lead to a hydrodynamic selection of initial chiral bias of supramolecular systems composed of exclusively achiral molecules within milliseconds. The self-assembled nuclei with the chirality sign affected by the shear force of enantiomorphic microvortices are subsequently amplified into almost absolutely chirality-controlled supramolecular gels or nanotubes. In contrast, turbulent vortices in stirring cuvettes fail to select the chirality of supramolecular gels. This study reveals that a laminar chiral microflow can induce enantioselection far from equilibrium, and provides an insight on the origin of natural homochirality., Symmetry breaking and chiral amplification are fundamental principles in chemistry and biology but the control of initial chiral bias remains a great challenge. Here the authors show that chiral microvortices can lead to a selection of initial chiral bias of supramolecular systems composed of achiral molecules.

An achiralC3-symmetric molecule was found to self-assemble into various hierarchical nanostructures such as nanotwists, nanotrumpets and nanobelts, in which the twisted fibers showed supramolecular chirality as well as circularly polarized luminescence although the compound is achiral.

The fabrication and application of supramolecular gels have achieved great progress in the past few decades. Although several reviews and books have well summarized the design, properties and functions of certain supramolecular gels, a comprehensive overview is still lacking to reveal the design strategy of the supramolecular gels. In this review, we propose a concept of a supramolecular gelaton, which is a structural unit or molecule for the design and construction of the supramolecular gels, to show how to design the targeted functional gels. We classify the gelaton into two types. One is a covalent gelaton that when covalently connects with other functional groups results in a molecule that can become a gelator. The other type is a non-covalent gelaton, which is a gelator molecule that can assist other gelator or non-gelator molecules to form gels. We hope that the concept of supramolecular gelatons will provide useful guidance and understanding of the design of gelator molecules and preparation of supramolecular gels.

Colloidal nanocrystal assemblies (CNAs) of cuprous oxide (Cu2O) are controllably synthesized by in-situ self-assembling primary Cu2O nanocrystals, in which Cu2O CNAs assemblied by nanocrystals of 8–10 nm were about 0.6 μm and Cu2O CNAs assemblied by nanocrystals of 32 nm were about 1.8 μm. From room temperature magnetization measurement results, both of the CNAs showed ferromagnetic behavior with very small saturation magnetization (Ms) values and 10 nm nanocrystal-based CNAs had the largest Ms value of about 9.2 emu/g. Electrochemical experimental results showed that submicron Cu2O CNAs were able to detect dopamine and uric acid quickly while micrometer Cu2O CNAs were not. Cu2O CNAs formed by 8 nm nanocrystals showed the highest electrocatalytic activity in oxygen reduction reaction and displayed the best adsorptive ability to remove Congo red in aqueous solutions, which can be recylced after a simple heat treatment. Furthermore, the formation mechanism and the relationship between crystalline size and assembly of primary nanocrystals as well as physicochemical properties of Cu2O CNAs have been discussed and analyzed.

Two types of PdCu2 nanoparticles were prepared through one-pot synthesis and a two-step reducing process, named as PdCu2-1 and PdCu2-2, respectively. The morphology and structure of as-prepared samples were investigated by transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and inductively coupled plasma-optical emission spectrometry. Results showed that more Pd atoms were buried in the inside of PdCu2-1, whereas more available Pd sites were distributed on the surface of PdCu2-2. The electrochemical measurements indicated that both PdCu2-1 and PdCu2-2 nanoparticles showed a higher electrocatalytic activity than that for pure Pd nanoparticles. In particular, PdCu2-2 predictably exhibited a better stability and durability as well as a lower onset potential and a higher catalytic current density than that of PdCu2-1 toward ethanol oxidation in alkaline media. On the basis of these studies, the formation mechanisms of both th...

This paper studies the electrochemical behaviors of symmetric supercapacitors with the porous carbon obtained from chestnut shells as active materials and ionic liquids as electrolytes, including 1-ethyl-3-methylimidazolium bis[(trifluoromethyl) sulfonyl]imide (EMImTF 2 N), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF 4 ) and 1-Butyl-3-methylimidazolium tetrafluoroborate (BMImBF 4 ). Experimental data observed at a current density of 0.1 A/g showed that symmetric supercapacitor using EMImBF 4 as the electrolyte had the maximum specific capacitance of 208.7 F/g, while 180.8 F/g for EMImTF 2 N and 134.6 F/g for BMImBF 4 . However, specific capacitance of supercapacitors assembled with EMImBF 4 , EMImTF 2 N and BMImBF 4 respectively retained 62.9%, 94.5% and 71.5% of the initial values after 2000 galvanostatic charge-discharge cycles. The relationship between the molecular structure of ionic liquids and electrochemical properties of the supercapacitors was discussed based on the experimental data.

Functionalization of carbon nanotubes (CNTs) has been proven to be an effective method to modulate their properties including electrocatalytic activity. Here, we report the catalytic properties of CNTs modified with various functional groups in the oxygen reduction reaction (ORR). Experimental data show that ORR activity of CNTs is enhanced markedly with increasing content of carboxyl groups, and MWNT-COOH sample display the highest current density and most positive onset potential among the studied catalysts. Remarkably, the functionalized CNTs exhibit excellent long-time stability and tolerance towards alcohols. Both experimental and theoretical results suggest that the deprotonated state of carboxyl groups promote the ORR electrocatalytic performance of CNTs in an alkaline electrolyte.

The electrochemical reduction behavior of nitrobenzene was studied on glassy carbon electrodes modified with MnFe 2 O 4 colloid nanocrystal assemblies. The crystalline size and structure of the colloid nanocrystal assemblies were found to play important roles in determining the catalytic activity of the electrode towards nitrobenzene. It was found that nitrobenzene was first reduced to phenylhydroxylamine via a four-electron reduction pathway, then phenylhydroxylamine was oxidized to nitrosobenzene by losing two-electron on the electrode. The electrochemical reaction mechanisms of p -nitrotoluene and m -dinitrobenzen on the electrodes were discussed and analyzed based on the experimental data.

The origin of biological homochirality, e.g., life selects the L-amino acids and D-sugar as molecular component, still remains a big mystery. It is suggested that mirror symmetry breaking plays an important role. Recent researches show that symmetry breaking can also occur at a supramolecular level, where the non-covalent bond was crucial. In these systems, equal or unequal amount of the enantiomeric nanoassemblies could be formed from achiral molecules. In this paper, we presented a brief overview regarding the symmetry breaking from dispersed system to gels, solids, and at interfaces. Then we discuss the rational manipulation of supramolecular chirality on how to induce and control the homochirality in the self-assembly system. Those physical control methods, such as Viedma ripening, hydrodynamic macro- and micro-vortex, superchiral light, and the combination of these technologies, are specifically discussed. It is hoped that the symmetry breaking at a supramolecular level could provide useful insights into the understanding of natural homochirality and further designing as well as controlling of functional chiral materials.

Stable luminescent π-radicals with doublet emission have attracted growing attention for functional molecular materials. However, their chiroptical properties, particularly their doublet emission-based circularly polarized luminescence, have never been investigated. Here, we investigate the circularly polarized luminescence (CPL) properties of a series of achiral luminescent open-shell π-radicals through various chirality regulation approaches, including induction by a magnetic field, supramolecular coassembly and chiral liquid crystal encapsulation.

By regulating the composition of solvents, the assembled nanostructures of chiral molecules transformed from 0D nanospheres to 3D nanoflakes, which showed significantly amplified circularly polarized luminescence., Achieving a higher dissymmetry factor is a crucial issue in developing circularly polarized luminescence (CPL) materials. Here, by tailoring the solvent composition and the morphology of the same chiral emissive small molecules (R- or S-SPAn), circularly polarized emission with a boosted dissymmetry factor (two orders) was realized. It was found that by regulating the water fraction in the mixed THF/H2O, we were able to achieve kinetic control over association of chiral emissive R- or S-SPAn into various nanostructures with 0D nanospheres, 2D nanoflakes and 3D stacked nanoflakes. These nanostructures are all CPL active. Remarkably, the dissymmetry factors of the nanostructures were significantly enhanced compared to those of the molecules and further boosted in different morphologies, from ∼10–4 (0D nanospheres) to 10–3 (2D flake) to ∼10–2 (3D nanoflakes). The enlarged glum value could be assigned to a good packing induced strong luminescence of an excimer. This strategy provides an efficient way to fabricate higher dissymmetry factor CPL organic nanomaterials by only changing the supramolecular architectures while using the same chiral small molecules.

In this work, lanthanide-doped upconversion nanoparticles (UCNPs) showing upconverted circularly polarized luminescence were demonstrated in an organic–inorganic co-assembled system. Achiral UCNPs (NaYF4:Yb/Er or NaYF4:Yb/Tm) can be encapsulated into chiral helical nanotubes through the procedure of co-gelation. These co-gel systems display intense upconverted circularly polarized luminescence (UC-CPL) ranging from ultraviolet (UV, 300 nm) to near-infrared (NIR, 850 nm) wavelength. In addition, the UV part of UC-CPL can be used to initiate the enantioselective polymerization of diacetylene.

Currently, the development of circularly polarized luminescent (CPL) materials has drawn extensive attention due to the numerous potential applications in optical data storage, displays, backlights in 3D displays, and so on. While the fabrication of CPL-active materials generally requires chiral luminescent molecules, the introduction of the "self-assembly" concept offers a new perspective in obtaining the CPL-active materials. Following this approach, various self-assembled materials, including organic-, inorganic-, and hybrid systems can be endowed with CPL properties. Benefiting from the advantages of self-assembly, not only chiral molecules, but also achiral species, as well as inorganic nanoparticles have potential to be self-assembled into chiral nanoassemblies showing CPL activity. In addition, the dissymmetry factor, an important parameter of CPL materials, can be enhanced through various pathways of self-assembly. Here, the present status and progress of self-assembled nanomaterials with CPL activity are reviewed. An overview of the key factors in regulating chiral emission materials at the supramolecular level will largely boost their application in multidisciplinary fields.

By constructing a supramolecular light-harvesting chiral nanotube in the aqueous phase, we demonstrate a cooperative energy and chirality transfer. It was found that a cyanostilbene-appended glutamate compound (CG) self-assembled into helical nanotubes exhibiting both supramolecular chirality and circularly polarized luminescence (CPL). When two achiral acceptors, ThT and AO, with different energy bands were co-assembled with the nanotube, the CG nanotube could transfer its chirality to both of the acceptors. The excitation energy could be transferred to ThT but only be sequentially transferred to AO. During this process, the CPL ascribed to the acceptor could be sequentially amplified. This work provides a new insight into the understanding the cooperative chirality and energy transfer in a chiral supramolecular system, which is similar to the natural light-harvesting antennas.

Palladium nanoparticle aggregates (Pd-NPAs) with various sizes were prepared by regulating the stability of Pd colloids. Structures of Pd-NPAs and their performances for electrooxidation of ethanol were investigated using power X-ray diffraction, transmission electron microscopy and electrochemical measurements. Experimental data illustrated that the size of Pd-NPAs, the concentration of electrolyte and the process of electrocatalysis jointly affected their electrocatalytic properties. The on-set potentials were negative-shifted during the electrocatalysis of ethanol as the concentration of KOH in the electrolytes continuously increased, while the catalytic current density reached the highest value in 2 M KOH electrolyte. The change of on-set potential, peak potential and peak current of Pd-NPAs during the electrooxidation of ethanol were systematically investigated and analyzed. A "size-electrolyte-process" mechanism was proposed to explain the variation of the electrocatalytic activity promoting in alkane media.

An achiral C3-symmetric molecule was found to self-assemble into various hierarchical nanostructures such as nanotwists, nanotrumpets and nanobelts, in which the twisted fibers showed supramolecular chirality as well as circularly polarized luminescence although the compound is achiral.

The electrochemical behavior of nitrobenzene and its derivatives at chemically-functionalized multi-wall carbon nanotubes (MWNTs) modified electrodes was studied. Experimental results showed that hydroxyl-containing MWNTs exhibited the highest electrocatalytic activity among the used MWNTs because of its weak capacitive features and oxygen-containing functional groups. The cycle voltammetrys of nitrobenzene derivatives on the MWNTs modified electrodes can be easily tuned by changing the substituted groups of nitrobenzene. Based on the experimental data, the electrochemical reaction mechanisms of nitrobenzene and its derivatives on the MWNTs modified electrodes have been discussed and analyzed.