Cyclic silanol derivatives (CSDs), possessing siloxane rings consisting of T-unit silicon and oxygen atoms, are considered efficient precursors for the preparation of versatile well-defined building blocks of hybrid materials such as cyclic, cage- or ladder-type SQs. This review provides an outline of the main synthetic routes to numerous stereoregular CSDs with different sizes of siloxane rings since the first example of CSDs reported by Brown et al. in 1965. The typical reaction conditions and chemical shifts of ²⁹Si NMR of all mentioned CSDs in this review are summarized in tables and schemes to recapitulate the state of the art. The synthesis of all-cis-cyclotetrasiloxanes (T₄), the most investigated CSDs, and their functionalization by different organic reactions to access various all-cis-T₄ with functional groups are methodically presented. Moreover, the potential of CSDs in multiple application fields is discussed to show the possible research directions of this family of compounds in the future.

Novel tetrathiol silsesquioxanes with double-decker or ladder nanocores are readily synthesized from their corresponding allyl counterparts. They constitute versatile building blocks for the preparation of hybrid organic–inorganic materials.

A vinyl-functionalized all-cis-tetrasiloxycyclotetrasiloxane [ViSi(OSiMe₂H)O]₄ (Vi = vinyl group) Janus precursor was prepared from potassium cyclotetrasiloxane silanolate. The Janus precursor was selectively modified at its dimethylhydrosilyl groups [–SiMe₂H] via the Piers–Rubinsztajn reaction to obtain a family of new tetravinyl-substituted Janus rings [ViSi(OR’)O]₄ containing various functional groups in moderate yields. Remarkably, the tetravinyl groups on the structure remained intact after modification by the Piers–Rubinsztajn reaction. Since these synthesized compounds possess multiple functional groups (up to eight per molecule), they are potential precursors for advanced hybrid organic-inorganic functional materials.

Tissue engineering scaffolds have been dedicated to regenerating damaged tissue by serving as host biomaterials for cell adhesion, growth, differentiation, and proliferation to develop new tissue. In this work, the design and fabrication of a biodegradable bilayer scaffold consisting of a ternary PLLA/PCL/CAB blend film layer and a PLGA/curcumin (CC) electrospun fiber layer were studied and discussed in terms of surface morphology, tensile mechanical properties, and molecular interactions. Three different compositions of PLLA/PCL/CAB—60/15/25 (TBF1), 75/10/15 (TBF2), and 85/5/10 (TBF3)—were fabricated using the solvent casting method. The electrospun fibers of PLGA/CC were fabricated using chloroform (CF) and dimethylformamide (DMF) co-solvents in 50:50 and 60:40 volume ratios. Spherical patterns of varying sizes were observed on the surfaces of all blend films—TBF1 (17–21 µm) > TBF2 (5–9 µm) > TBF3 (1–5 µm)—caused by heterogeneous surfaces inducing bubble nucleation. The TBF1, TBF2, and TBF3 films showed tensile elongation at break values of approximately 170%, 94%, and 43%, respectively. The PLGA/CC electrospun fibers fabricated using 50:50 CF:DMF had diameters ranging from 100 to 400 nm, which were larger than those of the PLGA fibers (50–200 nm). In contrast, the PLGA/CC electrospun fibers fabricated using 60:40 CF:DMF had diameters mostly ranging from 200 to 700 nm, which were larger than those of PLGA fibers (200–500 nm). Molecular interactions via hydrogen bonding were observed between PLGA and CC. The surface morphology of the bilayer scaffold demonstrated adhesion between these two solid surfaces resembling “thread stitches” promoted by hydrophobic interactions, hydrogen bonding, and surface roughness.