Chiral nanoparticles

There are a number of uses for chiral metallic nanoparticles. One such application for chiral nanoparticles are as chiral sensors. This is considered feasible as it has been already demonstrated that uncoated gold nanoparticles can show selective aggregation in the presence of D-tryptophan and copper ions while none in the presence of L-tryptophan and other aminoacids. ° Similar work was conducted for diols (Fig. 5) using functionalised gold nanoparticles and for the chiral dicationic helicene, helquat. ... 

Non-chiral nanoparticles were also of interest for sensing of optical activity through the enhancement of the chirality of molecules in the presence of the plasmonic field at the edge of, for example nanocubes or gold structures on surfaces. ... 

The fact that these chiral nanoparticles are able to encapsulate different types of inorganic and organic substances opens the door to new supramolecular assemblies with controlled size and tuneable chiral core/surface that can be of great interest in the future as functional matrices for encapsulation and recognition processes. 

Multi-walled CNTs (MWCNTs) are produced by arc discharge between graphite electrodes but other carbonaceous materials are always formed simultaneously. The main by-product, nanoparticles, can be removed utilizing the difference in oxidation reaction rates between CNTs and nanoparticles [9]. Then, it was reported that CNTs can be aligned by dispersion in a polymer resin matrix [10]. However, the parameters of CNTs are uncontrollable, such as the diameter, length, chirality and so on, at present. Furthermore, although the CNTs are observed like cylinders by transmission electron microscopy (TEM), some reports have pointed out the possibility of non-cylindrical structures and the existence of defects [11-14]. 

Possible applications of MIP membranes are in the field of sensor systems and separation technology. With respect to MIP membrane-based sensors, selective ligand binding to the membrane or selective permeation through the membrane can be used for the generation of a specific signal. Practical chiral separation by MIP membranes still faces reproducibility problems in the preparation methods, as well as mass transfer limitations inside the membrane. To overcome mass transfer limitations, MIP nanoparticles embedded in liquid membranes could be an alternative approach to develop chiral membrane separation by molecular imprinting [44]. 

Mixtures of a nematic liquid crystal (LC or LC ) with small quantities of gold nanoparticles coated with alkylthiolates (<5 wt%) including an alkylthiolate functionalized with a chiral group have been studied (Figure 8.29) [72]. All mixtures show nematic mesophases with transition temperatures and phase stability very similar to those oftheliquid crystal precursors LC or LC. The introduction ofachiral center into the mixtures (mixtures of Au ) produce chiral nematic mesophases. A similar result is obtained in mixtures of Au and LC doped with the chiral dopant (s)-Naproxen. 

A hydrosilylation/cyclization process forming a vinylsilane product need not begin with a diyne, and other unsaturation has been examined in a similar reaction. Alkynyl olefins and dienes have been employed,97 and since unlike diynes, enyne substrates generally produce a chiral center, these substrates have recently proved amenable to asymmetric synthesis (Scheme 27). The BINAP-based catalyst employed in the diyne work did not function in enyne systems, but the close relative 6,6 -dimethylbiphenyl-2,2 -diyl-bis(diphenylphosphine) (BIPHEMP) afforded modest yields of enantio-enriched methylene cyclopentane products.104 Other reported catalysts for silylative cyclization include cationic palladium complexes.105 10511 A report has also appeared employing cobalt-rhodium nanoparticles for a similar reaction to produce racemic product.46... 

The concept of using colloids stabilized with chiral ligands was first applied by Bonnemann to hydrogenate ethyl pyruvate to ethyl lactate with Pt colloids. The nanoparticles were stabilized by the addition of dihydrocinchonidine salt (DHCin, HX) and were used in the liquid phase or adsorbed onto activated charcoal and silica [129, 130]. The molar ratio of platinum to dihydrocinchonidine, which ranged from 0.5 to 3.5 during the synthesis, determines the particle size from 1.5 to 4 nm and contributes to a slight decrease in activity (TOF = l s ). In an acetic acid/MeOH mixture and under a hydrogen pressure up to 100 bar, the (R)-ethyl lactate was obtained with optical yields of 75-80% (Scheme 9.11). 

Although several noble-metal nanoparticles have been investigated for the enantiomeric catalysis of prochiral substrates, platinum colloids remain the most widely studied. PVP-stabilized platinum modified with cinchonidine showed ee-values >95%. Several stabilizers have been also investigated such as surfactants, cinchonidinium salts and solvents, and promising ee-values have been observed. Details of a comparison of various catalytic systems are listed in Table 9.16 in one case, the colloid suspension was reused without any loss in enantioselectiv-ity. Clearly, the development of convenient two-phase liquid-liquid systems for the recycling of chiral colloids remains a future challenge. 

Another method for assaying the activity and stereoselectivity of enzymes at in vitro concentrations is based on surface-enhanced resonance Raman scattering (SERRS) using silver nanoparticles (116). Turnover of a substrate leads to the release of a surface targeting dye, which is detected by SERRS. In a model study, lipase-catalyzed kinetic resolution of a dye-labeled chiral ester was investigated. It is currently unclear how precise the method is when identifying mutants which lead to E values higher than 10. The assay appears to be well suited as a pre-test for activity. 

Enzymatic polymerizations have been established as a promising and versatile technique in the synthetic toolbox of polymer chemists. The applicability of this technique for homo- and copolymerizations has been known for some time. With the increasing number of reports on the synthesis of more complex structures like block copolymers, graft copolymers, chiral (co)polymers, and chiral crosslinked nanoparticles, its potential further increases. Although not a controlled polymerization technique itself, clever reaction design and integration with other polymerization techniques like controlled radical polymerization allows the procurement of well-defined polymer structures. Specific unique attributes of the enzyme can be applied... 

Zero-Dimensional Nanoparticle Additives in the Chiral Nematic Phase... 

Several exciting phenomena described for non-chiral nematic systems were also reported for nanoparticle-doped chiral nematic liquid crystals. We mentioned the work of Kobayashi et al., who, most notably, demonstrated a frequency modulation twisted nematic (FM-TN) mode and fast switching characteristics using metal nanoparticles as dopants [301-307, 313, 314],... 

Our group pursued another approach of combining the properties of nanoparticles with chiral nematic liquid crystal phases. The idea was to decorate gold nanoparticles with chiral molecules known to be strong inducers of chiral nematic phases. To realize the idea, we prepared a series of alkylthiol-capped gold nanoparticles, either pure monolayer or mixed monolayer, with all or about every second of the alkylthiols end-functionalized with (5)-naproxen (e.g., 6 in Fig. 11) [349]. 

Fig. 10 (a, b) Schematic mechanism demonstrated for a reflective color M-paper with magnetically controllable characteristics, (c, d) The intensity of magnetic field dependence on the reflection spectra of chiral nematic mixtures doped with magnetite nanoparticles that are surface modified with oleic acid and a chiral pyridine-based dopant, as well as photographs of both formulations before and after a magnetic field of 1,000 GS was applied (see photograph insets above) [364], (Copyright 2010, Taylor Francis)... 

Earlier work on nanoparticle-doped chiral smectic-A (SmA ) and chiral smec-tic-C (SmC ) phases including some intriguing electro-optic effects in ferroelectric SmC phases were summarized in two earlier reviews [1, 2],... 

Fig. 11 Mixed monolayer alkylthiol-capped gold nanoparticle end-functionalized with (S)-naproxen chiral dopant moieties [349, 365, 366]...

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