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Abstract

Throughout the Middle Ages, Dubrovnik maintained active and regular commercial and maritime contacts with various cities and states of the Mediterranean. These activities led to the organisation of a health care system and the development of medicine. With respect to the economic, commercial and maritime aspects of the culture of this city state, Dubrovnik became open to the civilising progress of the region and period. The brief visit of the Mediaeval ophthalmologist, Master Samuel Ebrej supports this fact.

Exploring the Properties of H2O@C60 with the Local Second‐Order Møller‐Plesset Perturbation Theory: Blue or Red Shift in C60 and H2O Fundamentals to Expect?

“…Recent advances in the synthesis of endohedral fullerene complexes utilizing the so called “molecular surgery” approach [3–8] have significantly stimulated many experimental and theoretical investigations in this field leading to interesting and sometimes unexpected phenomena. For instance, the first synthesized complex with a molecular guest, H 2 @C 60 , [9,10] exhibited: a) the enhanced chemical reactivity related to quenching of singlet molecular oxygen, 1 O 2 , as compared to empty C 60 or H 2 ; [11] b) the unusual temperature dependence of the nuclear spin‐lattice relaxation time T 1 − close to that in dissolved H 2 ; [12] c) the five times larger value of proton relaxivity in the presence of paramagnet nitroxide radicals when compared to free H 2 ; [13] d) the possibility to stabilize and reversibly interconvert the two nuclear spin allotropic forms of encaged H 2 : ortho and para ; [14] e) a coupling of the quantized translational and rotational degrees of freedom of the encaged H 2 guest due to cage confinement leading to a tangled translation‐rotational energy level structure (see a recent review [15] and references therein) and f) a bond elongation of the encapsulated H 2 molecule resulting in a red shift of H 2 vibrational stretching frequency [16–20] …”

“…H 2 O@C 60 has been the subject of numerous spectroscopic investigations utilizing nuclear magnetic resonance, inelastic neutron scattering, infrared and terahertz spectroscopies [21,26–32] to elucidate the role of quantum effects in the dynamics of the encaged water molecule. Similar to H 2 @C 60 , the H 2 O@C 60 complex also demonstrates unusual nuclear spin relaxation, [30] ortho ‐ para spin conversion [26–28,31,33] (which influences the low‐temperature heat capacity of the complex [34] ), and strong quantum effects due to quantization of the guest's translational, rotational and vibrational degrees of freedom with the next coupling of translational‐rotational motions (for a more comprehensive discussion please refer to the recent articles [15,35,36] ). However, the global‐minimum structure of H 2 O@C 60 has not been unequivocally determined by various theoretical calculations up to now leading to an open question of the appearance of blue / red shifts in vibrational frequencies of the water molecules caused by encapsulation.…”

A Solid‐State Intramolecular Wittig Reaction Enables Efficient Synthesis of Endofullerenes Including Ne@C60, 3He@C60, and HD@C60

“…Noble gas endofullerenes encapsulating the 3 He or 129 Xe isotopes, with nuclear spin= , are potentially valuable as biosensors for detection by magnetic resonance, or as tools to monitor the course of fullerene reactions by NMR [11a–d] . Determining the quantised rotational and translational energy levels of an endohedral species, using inelastic neutron scattering and IR/THz spectroscopy, provides a powerful test of current models of non‐bonding interactions [12a–c] . Endofullerenes in which a trapped molecule exhibits nuclear spin isomerism are of importance for the study of spin isomer interconversion, allotrope enrichment, and have potential applications to chemical and clinical magnetic resonance [13] .…”