Both the arrest and thecreationofmovement are fundamental aspects of dynamics on macroscopic as well as microscopic levels. Brakes and motors dominate the operation of machines, be they those of daily life, such as vehicles and appliances, or those of living systems. like muscles and Ilagellae. On the molecular level motion is thenorm;spontanwus freerotationaroundsinglebonds is thus the rule, not the exception. In machines of ordinary experience, such as automobiles, the brake is often as important as the accelerator. We now report the first molecular analog: a reversible molecular brake. Figure I presents theconcept inbothgeneral andspecific terms. 1 (biako ofl) 3 (brako on) -"W 2 (brake ott) 4 (brake on) Figure 1. Conceptualandaetualdepictionoftheoperationofa molecular brake. With the brakedisengaged. the wheel-(a) representedasa threetoothed gear ( I ) and (b) constructed as a triptycene (2)' -spins rapidly. Engagement ofthe brake (3and4) slowsorstopsrotation. With the actual system, the brake is activated remotely (2 -4) by addition of Hg2+ ion. In the absence of Hgz+ (or other metal ions), the triptycene wheel spins rapidly a t 30 OC, as evidenced by the simplicity of the 'H NMR spectrum of 2 (Figure 2b). wherein by virtue of C, symmetry arising from relatively rapid rotation, the 12 triptycene aromatic protons give rise to only four sets (asterisked) of resonances. Addition of Hg(OzCCF3)z to 2 results in profound changes in the 30 OC (and other) 'H NMR spectrum (Figure 3a). Most noteworthy are the change in the extraordinarychemicalshiftoftheB-ringmethoxyin 2 (6 2.1 to a normal 6 4. I 3 value (not shown) and the obvious broadening of the four resonances attributable to the hydrogens in the three benzo rings of the triptycene. Variable-temperature 'H NMR experiments3 (see Figure 3) document the engagement of the brake. In particular, a t -30 OC (contrast Figure 2),thethreearomaticringsofthetriptyceneare nolongerequivalent becauseofthearrest ofrotation on theNMR . . ( I ) For the use of triptycenaas gean see, inter alia (a) Guenzi. A,: Johnson. C.(2) The 9-ring mcthary group is evidently (see models) in the shielding zone of the lriplycene knzo rings; the B-ring melhory group in 9 is similarly shielded (6 2.W).'(3) See supplementary material for specifis.
Theanine is a non-protein amino acid that occurs naturally in the tea plant (Camellia sinensis) and contributes to the favourable taste of tea. It is also associated with effects such as the enhancement of relaxation and the improvement of concentration and learning ability. It is also linked with health benefits including the prevention of certain cancers and cardiovascular disease, the promotion of weight loss and enhanced performance of the immune system. Thus, there has been a significant rise in the demand for theanine. While theanine has been chemically and biologically synthesised, techniques to isolate theanine from natural sources remain an important area of research. In this review article, the properties and health benefits of theanine are summarised and the synthesis and isolation of theanine are reviewed and discussed. Future perspectives for the isolation of theanine from natural sources are also outlined.
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