A 20-membered N2O2S2-macrocycle (L-1) and a 40-membered N4O4S4-macrocycle (L-2) were employed as a [1:1] and a [2:2] cyclization product, respectively, for the preparation of diverse types of supramolecular complexes including a cascade complex. Six complexes (1-6) of the smaller macrocycle L-1 including discrete to continuous forms, mono- to heteronuclear, and endo-to exo-and endo/ exocoordination were prepared and their coordination modes were discussed systemically. First, the reaction of L' with CuI in the presence of trifluoroacetic acid afforded an exocyclic 1-D coordination polymer 1[(mu(4)-Cu4I4)(HL1)(2)](cF(3)COO)(2)}(n), (1). Meanwhile, the reaction of L1 with Cu(ClO4)(2).6H(2)O afforded a typical endocyclic mononuclear complex [Cull(L1)](C104)2,-1-120 (2). In the reactions of L' with CdX2 (X = Br and I), isostructural sandwich-type complexes [Cd(L')2Br2] (3) and [Cd(12)(2)I-2] (4) were isolated. The treatment of L' with Hg(C104)2 also afforded a sandwich-type complex [Hg(L-1)(2)](ClO4)(2) (5). One-pot reaction of L' with a mixture of Hg12 and CdI2 afforded a dumbbell-type heteronuclear complex {[Cd(L-1)](2)(j4-Hg2I6)}[Hg2I6] (6), in which, the Cd(II) ion occupies the macrocyclic cavity. Further, such two endocyclic Cd(II) complex units are bridged by a square-type (y-Hg216)2-cluster remaining another same cluster separately. The comparative NMR data exhibited a higher affinity of Cd(II) over Hg(II) toward L1, in the parallel to the situation occurred in the solid state. Meanwhile, complexations of the extra-large macrocycle L2 is more challenging to afford some interesting dimercury(II) coordination products including a cascade complex. In solution, the dimercury(II) perchlorato complex of L2 as a metalloligand shows a preferential binding of dabco (1,4-diazabicyclo[2,2,2]octane), but its dimercury(II) iodo complex has a much smaller affinity for dabco. In order to explain these results, the solid dimercury(II) complexes with different anions [Hg-2(L-2)X-4] (7: X = I, 8: X = ClO4) were prepared and characterized. Further, the dimercury(II) perchlorato complex 8 reacts with dabco to forms a cascade complex [Hg-2(L-2)(mu-dabco)(ClO4)(2)](ClO4)(2).2DMF.2ether (9), exhibiting its formation being metal-driven and coordinated anion-regulated. The observed cascade complexation both in solution and solid states is an example of the adaptive guest binding.

Background: Caudal-related homeobox transcription factor 2 (CDX2) is an intestine-specific transcription factor implicated in tumour differentiation, proliferation, cell adhesion and migration. Negative CDX2 status (CDX2-) is associated with worse prognosis in colorectal cancer and may identify high-risk stage II disease that benefits from adjuvant chemotherapy. This observational study investigated whether CDX2- is associated with prognosis or response to chemotherapy in the mismatch repair-deficient (dMMR) phenotype of colorectal cancer. Methods: Patients with resectable dMMR colorectal cancer were eligible for inclusion. The prognostic and predictive value of CDX2 expression on the presence of lymph node metastasis (LNM) and survival was investigated. CDX2 status was determined via immunohistochemistry using the Leica Bond (TM) CDX2 (clone EP25) ready-to-use primary antibody. Results: Some 235 of 238 consecutive dMMR tumours were assessed for CDX2 status. CDX2- was observed in 15.7 per cent of colorectal cancer. Interobserver agreement was excellent (kappa = 0.863; P < 0.001). CDX2- was significantly associated with female sex, increased size, advanced stage, worse conventional and poorly differentiated cluster (PDC) grade, mucinous morphology, perineural and lymphovascular invasion, and pN status (all P <= 0.038). CDX2- was not associated with LNM or survival in multivariable analysis. Independent predictors of LNM were PDC grade (odds ratio (OR) 4.12, 95 per cent c.i. 1.76 to 9.63; P = 0.001) and extramural venous invasion (OR 3.79, 1.62 to 8.85; P = 0.002). Budding (hazard ratio (HR) 2.79, 95 per cent c.i. 1.60 to 4.87; P < 0.001), pT status (HR 3.59, 1.29 to 10.01; P = 0.015) and adjuvant chemotherapy (HR 2.07, 1.15 to 3.74; P = 0.016) were independently associated with worse disease-free survival. Conclusion: CDX2- does not confer a worse prognosis in the dMMR phenotype of colorectal cancer. The MMR status of patients with colorectal cancer should be determined before assessing CDX2 status.