Mimicry unveiled: The challenging diagnosis of pigmented purpura-like mycosis fungoides initially misdiagnosed as pigmented purpura.

Key Clinical Message: Unlike most cases, the lesions were localized to the dorsum of the hand, lacked pruritus (itching), and did not exhibit "sperm-like blood vessels," which are typically pathognomonic to classical MF. Abstract: The study presents a rare case involving a 44-year-old woman who developed a skin condition on the base of her left thumb. Initially misdiagnosed as pigmented purpura, the need for further investigation arose to determine the nature of the condition accurately. The medical evaluation encompassed a comprehensive analysis of the patient's skin ailment. A series of diagnostic examinations were conducted to ascertain the underlying cause. Although routine blood tests yielded unremarkable results, the distinct characteristics of the rash prompted a more thorough investigation. Subsequent assessment revealed that the skin condition was not pigmented purpura, as initially presumed, but rather a manifestation of cutaneous T-cell lymphoma (CTCL) known as mycosis fungoides (MF). MF is an infrequent lymphoma predominantly affecting individuals aged 45-65, exhibiting a male-to-female sex ratio of 2:1. The annual incidence of MF ranges from 0.3 to 0.96 cases per 100,000 individuals. The woman's skin exhibited discrete patches adorned with colored dots, progressively thickening and pigmentation. Notably, the absence of pruritus did not dispel suspicion. This case underscores the significance of accurately diagnosing uncommon dermatological disorders to facilitate appropriate medical intervention. The unique appearance of the rash and its distinctive features, despite normal blood results, enabled the identification of MF. The patient's treatment encompassed a combination of steroids and narrowband UV therapy. Vigilance, continued research, and heightened awareness are paramount for early intervention and improved patient outcomes. Such efforts contribute to an enhanced understanding of the complexities of this condition.

CdS-Based Catalysts Derived from TMeQ[6]/[CdxCly]n--Based Frameworks for Oxidation Benzylamine.

The anion-induced outer surface interaction of Q[n]s is an important driving force in the construction of Q[n]-based supramolecular frameworks. In this work, a symmetric tetramethyl-substituted cucurbit[6]uril (TMeQ[6]) is selected as the basic structural block. Using the anion-induced outer surface interaction of Q[n]s derived from [CdxCly]n- anions formed by Cd2+ cations in a HCl medium, four different TMeQ[6]-[CdxCly]n--based supramolecular frameworks are constructed. Three of the most common TMeQ[6]-[CdxCly]n--based supramolecular frameworks are selected for further vulcanization, and three different CdS/TMeQ[6]-based framework catalysts with different structures and properties are obtained. The catalytic activities of these three CdS/TMeQ[6]-based framework catalysts are investigated by the coupling photocatalytic reaction of aminobenzyl, and the results showed that the catalytic activities of the three catalysts are all higher than that of pure CdS. Therefore, this work establishes that it is possible to establish a method for synthesizing the Q[n]-based framework-supported catalysts by first synthesizing TMeQ[6]-[CdxCly]n--based supramolecular frameworks and then forming Q[n]-based framework supported catalysts by sulfurization or reduction.

Cucurbit[n]uril-Based Supramolecular Frameworks Assembled through Outer-Surface Interactions.

Porous materials, especially metal-organic frameworks, covalent organic frameworks, and supramolecular organic frameworks, are widely used in heterogeneous catalysis, adsorption, and ion exchange. Cucurbit[n]urils (Q[n]s) suitable building units for porous materials because they possess cavities with neutral electrostatic potential, portal carbonyls with negative electrostatic potential, and outer surfaces with positive electrostatic potential, which may result in the formation of Q[n]-based supramolecular frameworks (QSFs) assembled through the interaction of guests within Q[n]s, the coordination of Q[n]s with metal ions, and outer-surface interaction of Q[n]s (OSIQ). This review summarizes the various QSFs assembled via OSIQs. The QSFs can be classified as being assembled by 1) self-induced OSIQ, 2) anion-induced OSIQ, and 3) aromatic-induced OSIQ. The design and construction of QSFs with novel structures and specific functional properties may establish a new research direction in Q[n] chemistry.

Outer surface interactions to drive cucurbit[8]uril-based supramolecular frameworks: possible application in gold recovery.

Q[8]-based honeycomb-like frameworks can be obtained in [AuCl4]--free aqueous HNO3 solution and aqueous HCl and HNO3 solutions that contain [AuCl4]-. The outer surface interaction of Q[8] with planar inorganic anions [AuCl4]- and NO3- is the main driving force. These frameworks exhibit a high selectivity for imprisoning [AuCl4]- that could establish a process for gold recovery.

Coordination supramolecular assemblies of a monohydroxycucurbit[7]uril and their potential applications in gas sorption.

Coordination supramolecular assemblies of monohydroxycucurbit[7]uril ((HO)Q[7]) with alkaline earth metal ions (AE2+) have been formed in aqueous HCl solution in the presence of tetrachloride cadmium anions ([CdCl4]2-) as a structure directing agent. The driving force for the assembly could be attributed to the interaction of the positive electro-potential outer-surface of (HO)Q[7] molecules with [CdCl4]2- anions and ionic dipole interaction of the hydroxyl of (HO)Q[7] molecules with [CdCl4]2- anions. Moreover, the porous structure of the (HO)Q[7]/AE2+-based coordination supramolecular assemblies could result in potential applications in the selective sorption of polar volatile organic molecules, which may be useful in molecular sieves, sensors, absorption and separation.

Hexamethylcucurbit[3,3]uril-Based Porous Supramolecular Assemblies and Their Adsorption Properties.

In the present work, we selected hexamethylcucurbit[3,3]uril (Me6Q[3,3]) as a building block and obtained two Me6Q[3,3]-based porous supramolecular assemblies from neutral water (A) and aqueous HCl solutions (B), respectively. Both Me6Q[3,3]-based assemblies are constructed of Me6Q[3,3] molecules through the typical outer surface interaction of cucurbit[n]urils, as well as hydrogen bonding between latticed water molecules and portal carbonyl oxygens of Me6Q[3,3]. The assemblies present different porous structure features and exhibit different adsorption properties for eight common volatile organic compounds. However, the two porous assemblies exhibit similar adsorption properties for certain fluorophore dyes, including rhodamine B (G1), fluorescein (G2), and pyrene (G3), and form solid colored fluorescent compounds, some of which exhibit responses to the selected volatile organic compounds.

Mono- and Dihydroxylated Symmetrical Octamethylcucurbiturils and Allylated Derivatives.

Mono- and dihydroxylated symmetrical octamethylcucurbit[6]urils {(OH)OMeQ[6] and (OH)2OMeQ[6]} were prepared using a photochemical method to introduce limited alcohol group(s) directly to the parent symmetrical octamethylcucurbit[6]uril (OMeQ[6]), and the resulting compounds were verified by 1H NMR, Xevo Q-TOF MS, and X-ray crystallography. Further chemical modification of mono- and dihydroxylated OMeQ[6] was also performed.

Twisted Cucurbit[n]urils.

Two new twisted cucurbiturils, cucurbit[13]uril (tQ[13]) and cucurbit[15]uril (tQ[15]), have been synthesized and separated, and their structures have been confirmed by NMR spectroscopy and MALDI-TOF mass spectrometry together with the X-ray structures of two new complexes, {Dy(H2O)4Cd(H2O)4tQ[13]}·2.5[CdCl4]·65H2O and {Cd0.5(H2O)2tQ[15]}·[CdCl4]·47H2O. tQ[15] is the largest cucurbit[n]uril (Q[n]) in the Q[n] family reported to date. The X-ray diffraction studies of both complexes indicated that these large tQ[n]s effectively exhibit two different cavities-a central cavity and two side cavities. Preliminary host-guest behavior by each of the new systems was investigated by NMR studies.

Synthesis and separation of cucurbit[n]urils and their derivatives.

Cucurbit[n]uril chemistry has become an important part of contemporary supramolecular chemistry since cucurbit[n]urils (Q[n]s) are not only able to encapsulate various guests, but are also capable of coordinating to a wide range of metal ions, leading to the establishment of Q[n]-based host-guest chemistry and coordination chemistry. Each of these impressive developments can be attributed to the growth of protocols for obtaining Q[n]s. In this review, we survey synthetic procedures for obtaining cucurbit[n]urils and their substituted derivatives together with the separation and purification of these remarkable compounds. The coverage is aimed at both existing workers in the field as well as at those requiring an "entry" into Q[n]-based research.

Encapsulation of alkyldiammonium ions within two different cavities of twisted cucurbit[14]uril.

Binding interactions between twisted cucurbit[14]uril (tQ[14]) and a series of alkyldiammonium ions both in aqueous solution and DMSO media were investigated by NMR spectroscopy and ITC. Experimental data indicate that tQ[14] possesses two kinds of cavities with different space environments, which can encapsulate two or even three guest molecules with suitable shape and size.

[The Interaction of Cucurbit[8]uril with Thionine and Carbendazim with Spectroscopic Method].

In this paper, the interaction of cucurbit [8]uril(Q[8]) with thionine (TH) and carbendazim (CBZ) were investigated with fluorescence and UV-Vis spectroscopy. The experimental results showed that the inclusion complex between Q[8] and TH informed was at molar ratios of 1∶2 in 0.01 mol·L-1 hydrochloric acid solution. The fluorescence intensity of the Q[8]/TH complexes quenched when Q[8] was added to TH solution, but fluorescence increasing of the Q[8]/TH complex with the addition of CBZ was observed. The fluorescence increasing values show a good linear relationship with the CBZ concentration within 0~3.5 µmol·L-1. The linear regression equation relating fluorescence intensity (If) to CBZ concentration (c) is If=0.45c+32.24 (r=0.999). The detection limit was 9.39×10-8 mol·L-1. Forthemore, the influence of foreign species on the analytical signal of the Q[8]/TH complex in the presence of carbendazim was established. No interference was observed from commonly used foreign species such as metal ions (Fe3+, Mg2+, Ca2+). In particular, benzimidazole compounds thiabendazole and fuberidazole do not interfere with CBZ determination at a specific concentration. The results revealed that complexation of Q[8] and TH with CBZ offers a fluorescent switching "on-off" effect which will supply a potential application in pesticide residues test.

A Hemimethyl-Substituted Cucurbit[7]uril Derived from 3α-Methyl-glycoluril.

A novel hemimethyl-substituted cucurbit[7]uril (HMeQ[7]) derived from 3α-methyl-glycoluril has been prepared. HMeQ[7] is readily soluble in both water and dimethyl sulfoxide (DMSO) and displays not only host-guest interaction properties similar to those of the normal cucurbit[7]uril but also unusual properties in DMSO.

A novel shell-like supramolecular assembly of 4,4'-bipyridyl derivatives and a twisted cucurbit[14]uril molecule.

This work showed that the 4,4'-bipyridyl group and alkyl chains of 4,4'-bipyridyl derivatives are completely located in the shell-like cavity of the twisted cucurbit[14]uril molecule and formed novel shell-like 1 : 1 inclusion complexes. As it is enthalpy-driven the complexation benefits from ion-dipole interactions.

Encapsulation of haloalkane 1-(3-chlorophenyl)-4-(3-chloropropyl)-piperazinium in symmetrical α,α',δ,δ'-tetramethyl-cucurbit[6]uril.

Complexation of haloalkane 1-(3-chlorophenyl)-4-(3-chloropropyl)-piperazinium (PZ(+)) dihydrochloride with symmetrical α,α',δ,δ'-tetramethyl-cucurbit[6]uril (TMeQ[6]) has been investigated using NMR spectroscopy, MALDI-TOF mass spectrometry, isothermal titration calorimetry (ITC), and X-ray crystallography. Our data indicate that the chloropropyl group of PZ(+) resides within the cavity of TMeQ[6] in both aqueous solution and the solid state, generating a highly stable inclusion complex PZ(+)@TMeQ[6]. In aqueous solution, the formation of the inclusion complex PZ(+)@TMeQ[6] benefits from the ion-dipole interactions between the guest PZ(+) and the host TMeQ[6]. While in the solid state, hydrogen-bonding interactions also play an important role in stabilizing the inclusion complex PZ(+)@TMeQ[6].

Coordination of alkaline earth metal ions in the inverted cucurbit[7]uril supramolecular assemblies formed in the presence of [ZnCl4]2- and [CdCl4]2-.

A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water-soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H(+) form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE(2+)) in aqueous HCl solutions in the presence of [ZnCl(4)](2-) and [CdCl(4)](2-) anions as structure-directing agents. Single-crystal X-ray diffraction analysis revealed that both iQ[7]-AE(2+) -[ZnCl(4)](2-) -HCl and iQ[7]-AE(2+) -[CdCl(4)](2-) -HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl(4)](2-) and [CdCl(4)](2-) anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE(2+) coordination polymers through outer-surface interactions of Q[n]s.

[Interaction of Cucurbit[8]uril with ß-Indoleacetic Acid and Methylviologen].

The interaction between Q[8] with ß-indoleacetic acid and the methylviologen was studied in aqueous solution with electronic absorption spectroscopy (UV-Vis), fluorescence spectroscopy, 1H NMR spectroscopy and isothermal titration calorimetry (ITC) in details. The authors explored the mode of action, action site and thermodynamic properties of the host-guest system. The electronic absorption and fluorescence spectroscopy data showed that the Q[8]/IAA system and Q[8]/MV²âº system informed 1:1 inclusion complexes in aqueous solution. ITC results showed that the changes of Gibbs free energy and enthalpy are all negative, it suggested that complex formation was spontaneous and exothermic reaction. Moreover, ITC results for the Q [8] and IAA with MV²âº indicate that the association constants of the Q[8]-IAA and Q[8]-MV²âº complexes were (3.22 ± 0.96) x 105 L · mol⁻¹ and (3.90 ± 0.91) x 106 L · mol⁻¹, respectively. Therefore, the interaction between Q[8] and IAA with the MV²âº was a competitive process. This likely occurs because the MV²âº and IAA molecules attempt to occupy the Q[8] cavity, which reduces the fluorescence and absorption spectra intensity of Q[8]-IAA because of the formation of a new inclusion complex between Q[8] and IAA with MV²âº. In addition, with the addition of MV²âº to a Q[8]/IAA complex, 1H NMR results showed that the indole moieties of ß-indoleacetic acid and bipyridyl group of methylviologen can be incorporated into Q[8] cavities because of electronic transfer MV²âº with PQ in a Q[8] cavity with ternary complexes. These results provides the potential applications for the supramolecular self-assembly in cucurbit[n]urils field.

Interaction of Ln3+ with Methyl-Substituted Cucurbit[n]urils (n=5,6) Derived from 3α-Methyl Glycoluril.

The interactions between a series of lanthanide cations (Ln3+ ) and methyl-substituted cucurbiturils (SPMeQ[5] and SHMeQ[6]) derived from a 3α-methyl glycoluril have been investigated. Single-crystal X-ray diffraction analysis revealed that both SPMeQ[5] and SHMeQ[6] selectively interact with certain lanthanide ions. SPMeQ[5] forms coordination capsules in the presence of [CdCl4 ]2- . The Ln3+ cations that interact are the four light lanthanides, La3+ , Ce3+ , Pr3+ , and Nd3+ , whereas the remaining lanthanide cations remain in solution. SHMeQ[6] formed adducts of SHMeQ[6] with aqua complexes of lanthanide cations ([Ln(H2 O)8 ]3+ ); for SHMeQ[6]-Ln(NO3 )3 -CdCl2 -HCl systems (Ln=Gd-Lu), no solid crystals were obtained from systems that contained La, Ce, Pr, Nd, Sm, or Eu. Whereas solid crystals of adducts of SHMeQ[6] with aqua complexes of lanthanide cations (Ln=Sm-Lu) formed SHMeQ[6]-Ln(NO3 )3 systems in neutral solution, no solid crystals were obtained from systems that contained La, Ce, Pr, or Nd. These results suggest that SPMeQ[5]- and SHMeQ[6]-Ln(NO3 )3 systems could be useful for the selective isolation of these lighter or heavier lanthanide cations from mixtures. Energy-dispersive spectrometry indicated that the lighter or heavier lanthanide cations could be isolated from their heavier or lighter counterparts through interaction with SPMeQ[5] and SHMeQ[6].

Extended and contorted conformations of alkanediammonium ions in symmetrical α,α',δ,δ'-tetramethylcucurbit[6]uril cavity.

Binding interactions between symmetrical α,α',δ,δ'-tetramethylcucurbit[6]uril (TMeQ[6]) and a series of alkyldiammonium ions in aqueous solution and in the solid state were investigated by (1)H NMR spectroscopy, MALDI-TOF mass spectrometry, X-ray crystallography, and isothermal titration calorimetry (ITC). Their (1)H NMR spectra reveal that the actual binding behaviors vary depending upon the alkyl chain length. Their single-crystal X-ray diffraction analyses indicate the guest 1,2-ethanediammonium is located outside of the TMeQ[6] portal, while the other four alkyldiammonium guests can be accommodated in the TMeQ[6] cavity, forming 1:1 inclusion complexes. Most importantly, the long-chain alkyldiammoniums (1,8-octanediammonium and 1,10-decanediammonium) take a contorted conformation when bound within the TMeQ[6] cavity. Additionally, ITC experiments show that the complexation of the alkyldiammonium guests with TMeQ[6] is mainly enthalpy driven, which benefits from ion-dipole interactions.

Self-assemblies based on the "outer-surface interactions" of cucurbit[n]urils: new opportunities for supramolecular architectures and materials.

Supramolecular architectures and materials have attracted immense attention during the last decades because they not only open the possibility of obtaining a large variety of aesthetically interesting structures but also have applications in gas storage, sensors, separation, catalysis, and so on. On the other hand, cucurbit[n]urils (Q[n]s), a relatively new class of macrocyclic hosts with a rigid hydrophobic cavity and two identical carbonyl fringed portals, have attracted much attention in supramolecular chemistry. Because of the strong charge-dipole and hydrogen bonding interactions, as well as hydrophobic and hydrophilic effect derived from the negative portals and rigid cavities of Q[n]s, nearly all research in Q[n]s has been focused on utilizing the portals and cavities to construct supramolecular assemblies similar to other macrocyclic receptors such as cyclodextrin and calixarenes. Interestingly, a recent study revealed that other weak noncovalent interactions such as hydrogen bonding and π···π stacking, as well as C-H···π and ion-dipole interactions, could also be defined as "outer-surface interactions", which are derived from the electrostatically positive outer surface of Q[n]s. These interactions could be the driving forces in the formation of various novel Q[n]-based supramolecular architectures and functional materials. In this Account, we provide a comprehensive overview of supramolecular self-assemblies based on the outer-surface interactions of Q[n]s. These outer-surface interactions include those between Q[n]s, Q[n]s and aromatic molecules, Q[n]s and calixarenes, Q[n]s and inorganic complex ions, and Q[n]s and polyoxometalates. Pioneering work has shown that such weak noncovalent interactions play very important roles in the formation of various Q[n]-based functional materials and supramolecular architectures. For example, hydrogen bonds in outer-surface interactions between Q[n] molecules not only function as the sole driving force in the formation of one-dimensional Q[n] porous channels but also assist the bonding forces of the channels in capturing and accommodating acetylene molecules and carbon dioxide in the channel cavities. Moreover, upon introduction of a third species such as an aromatic molecule or inorganic anion into the Q[n]/metal system, "outer-surface interactions" could lead to Q[n]/metal-based self-assemblies from simple finite supramolecular coordination complexes to infinite polydimensional supramolecular architectures and other structures. Overall, this Account focuses on the novel self-assembly driving force derived from Q[n]s including (i) concepts of the outer-surface interactions of Q[n]s, (ii) providing plausible explanations of the mechanisms of the outer-surface interactions of Q[n]s, and (iii) introduction of an overview of the developments and practical applications of outer-surface interactions of Q[n]s in supramolecular chemistry. It is hoped that this study based on the outer-surface interactions of Q[n]s can enrich the field of molecular engineering of functional supramolecular systems and provide new opportunities for the construction of functional materials and architectures.

[CdCl4]2- anion-induced coordination of alkaline earth metal ions to cucurbit[7]uril, corresponding supramolecular self-assemblies and potential application.

In the present work, we describe three cucurbit[7]uril-based coordination supermolecular self-assemblies in the presence of [M(trans)Cl4](2-). It can affect the construction of Q[7]/metal ions-based coordination polymers, at the same time it can result in the formation of Q[7]-based supramolecular assemblies when introducing the [M(trans)Cl4](2-) into the Q[7]/metal ions system.