Tetraphenylethene-modified polysiloxanes: Synthesis, AIE properties and multi-stimuli responsive fluorescence.

Herein, polysiloxane-based aggregation-induced emission (AIE) polymers and rubbers were prepared which display interesting multi-stimuli responsive fluorescence. TPE-modified polydimethylsiloxanes (PDMS-TPE) as polysiloxane-based AIE polymers were synthesized through Heck reaction of bromo-substituted tetraphenylethene (TPE-Br) and vinyl polysiloxanes. As expected, TPE moiety endows the modified polysiloxane with typical AIE behavior. However, limited by the long polymer chains, the aggregation process of PDMS-TPE shows obvious differences compared with the small molecule TPE-Br. The fluorescence of PDMS-TPE in THF/H2O starts to increase when the H2O fraction (fw) is 70% while TPE-Br is nearly non-luminous until the fw is up to 99%. The fluorescence intensity ratio (I/I0) of PDMS-TPE in the aggregated state and dispersed state is over 1300, greater than that of TPE-Br (I/I0 = 380). More importantly, the exceptional thermal motion of Si-O-Si chains and AIE characteristic of TPE moiety work together, enabling PDMS-TPE to show specific temperature-dependent fluorescence with a wider response range of room temperature to 190°C, which is distinguished from TPE-Br. And such fluorescence responsiveness possess good fatigue-resistance. Furthermore, fluorescent silicone rubbers, r-PDMS-TPE were prepared by using PDMS-TPE as additive of the base gum. They display interesting solvent-controllable fluorescence and higher tensile strength (4.42 MPa) than the control sample without TPE component (1.96 MPa). Notably, a unique stretching-enhanced emission (SEE) phenomenon is observed from these TPE-modified silicone rubbers. When being stretched, the rubbers' fluorescent emission intensity could increase by 143%.

Novel low-shrinkage dental resin containing microcapsules with antibacterial and self-healing properties.

Dental resin restorations commonly fail because of fractures and secondary caries. The aim of this research was to synthesize a novel low-shrinkage dental resin with antibacterial and self-healing properties. The low-shrinkage dental resin was obtained by incorporating a 20 wt% anti-shrinkage mixture of an expanding monomer 3,9-diethyl-3,9-dimethylol -1,5,7,11-tetraoxaspiro[5,5] undecane and an epoxy resin monomer diallyl bisphenol A diglycidyl ether (1:1, referred as "UE") and different mass fractions of self-healing antibacterial microcapsules (0%, 2.5%, 5%, 7.5%, and 10%) were incorporated into the matrix to prepare multifunctional dental resin. Polymerization shrinkage, mechanical properties, antibacterial activity, self-healing ability, and cytotoxicity of this dental resin were evaluated. The polymerization volumetric shrinkage of resin containing 20 wt% UE and 7.5 wt% microcapsules was reduced by 30.12% (4.13% ± 0.42%) compared with control. Furthermore, it exhibited high antibacterial activity and a good self-healing efficiency of 71% without adversely affecting the mechanical property and cell viability. This novel multifunctional dental resin with low polymerization shrinkage and excellent antibacterial activity and self-healing capability has potential application as a dental resin material to decrease the incidence of fractures and secondary caries.

Novel antimicrobial and self-healing dental resin to combat secondary caries and restoration fracture.

OBJECTIVE: Dental resin composites have been the most popular materials for repairing tooth decay in recent years. However, secondary caries and bulk fracture are the major hurdles that affect the lifetime of dental resin composites. This current study synthesized a novel antimicrobial and self-healing dental resin containing nanoparticle-modified self-healing microcapsules to combat secondary caries and restoration fracture. METHODS: Multifunctional dental resins containing 0-20% nanoparticle-modified self-healing microcapsules were prepared. The water contact angle, antimicrobial properties, mechanical properties, cell toxicity, and self-healing capability of the dental resins were tested. RESULTS: A novel multifunctional dental resin was synthesized. When the microcapsule mass fraction was 10%, the resin presented a strong bacteriostasis rate (80.3%) and excellent self-healing efficiency (66.1%), while the hydrophilicity, mechanical properties, and cell toxicity were not affected. SIGNIFICANCE: The novel antimicrobial self-healing dental resin is a promising candidate for use in clinical practice, which provides a simple and highly efficient strategy to combat secondary caries and restoration fracture. This novel dental resin also gives the inspiration to prolong the service life of dental restorations.

Effects of thermal cycling on bonding properties of novel low-shrinkage resin adhesive.

OBJECTIVES: The current study aimed to investigate the bonding properties of a novel low-shrinkage resin adhesive containing expanding monomer and epoxy resin monomer after thermal cycling aging treatment. METHODS: Expanding monomer of 3,9-diethyl-3,9-dimethylol-1,5,7,11-tetraoxaspiro-[5,5] undecane (DDTU) as an anti-shrinkage additive and unsaturated epoxy monomer of diallyl bisphenol A diglycidyl ether (DBDE) as a coupling agent were synthesized. A blend of DDTU and DBDE at a mass ratio of 1∶1, referred to as "UE", was added into the resin matrix at the mass fraction of 20% to prepare a novel low-shrinkage resin adhesive.Then, the methacrylate resin adhesive without UE was used as the blank control group, and a commercial resin adhesive system was selected as the commercial control group. Moreover, the resin-dentin bonding and micro-leakage testing specimens were prepared for the thermal cycling aging treatment. The bonding strength was tested, the fracture modes were calculated, the bonding fracture surface was observed by scanning electron microscope (SEM), and the dye penetration was used to evaluate the tooth-restoration marginal interface micro-leakage. All the data were analyzed statistically. RESULTS: After aging, the dentin bonding strength of the experimental group was (19.20±1.03) MPa without a significant decrease (P>0.05), that of the blank control group was (11.22±1.48) MPa with a significant decrease (P<0.05) and that of the commercial control group was (19.16±1.68) MPa without a significant decrease (P>0.05). The interface fracture was observed as the main fracture mode in each group after thermal cycling by SEM. The fractured bonding surfaces of the experimental group often occurred on the top of the hybrid layer, whereas those of the blank and commercial control groups mostly occurred on the bottom of the hybrid layer. Micro-leakage rating counts of specimens before and after thermal cycling were as follows: the experimental group was primarily 0 grade, thereby indicating that a relatively ideal marginal sealing effect could be achieved (P>0.05); meanwhile, the blank control group was primarily 1 grade, and the penetration depth of dye significantly increased after thermal cycling (P<0.05); the commercial control group was primarily 0 grade without statistical difference before and after thermal cycling (P>0.05), while a significant difference was observed between the commercial control group and experimental group after thermal cycling (P<0.05). CONCLUSIONS: The novel low-shrinkage resin adhesive containing 20%UE exhibited excellent bonding properties even after thermal cycling aging treatment, thereby showing a promising prospect for dental application.

Bioinspired fluorescent molecules realize super bright blue luminescence under sunlight.

In recent years, non-aromatic fluorescent materials have attracted widespread attention, but achieving a high quantum yield (QY) in their dilute solutions still remains a challenge. In this work, inspired by the Clustering-triggered emission (CTE) phenomenon of non-aromatic amino acids and poly(amino acids), we successfully designed a bioinspired molecule with a dipeptide-like structure and active silanol groups. The as-prepared bioinspired molecule can be hydrolyzed by simple heating to obtain the hydrolysate h-PDs, which can emit strong blue fluorescence in dilute solution. And this was the first time to realize the emission behavior of non-aromatic fluorescent materials under sunlight. The QY of h-PDs in aqueous solution and solid state were as high as 98.2% and 96.3%, respectively, which were attributed to the condensation of active silanol groups at the end of the molecule, and the existence of hydrogen bonds and N â†’ Si coordination bonds that made small molecules cross-linked and aggregated into dense clusters. Finally, the application of h-PDs in the detection of intracellular and exogenous Hg2+ and Cys and luminescent films were also explored. Significantly, this work provides a design strategy for synthesizing high-fluorescence QY non-aromatic fluorescent materials, and verifies their potential application value in the fields of environment, biology and light-emitting devices.

Novel antibacterial dental resin containing silanized hydroxyapatite nanofibers with remineralization capability.

OBJECTIVES: Secondary caries is the primary issue that causes restoration failure. The objectives of this study were to: (1) synthesize silanized hydroxyapatite nanofibers loaded with erythromycin (s-HAFs@EM); (2) evaluate the mechanical property, antibacterial activity, and remineralization capability of the novel dental resin containing s-HAFs@EM. METHODS: s-HAFs were prepared by the solvothermal approach and loaded with EM. Characterization and antibacterial activity were evaluated. Subsequently, s-HAFs@EM were incorporated into dental resin at different mass fractions (5 %, 10 %, 15 %, and 20 %), and then they were submitted to characterization, including mechanical property, antibacterial activity, remineralization capability, and cytotoxicity. RESULTS: s-HAFs@EM were successfully synthesized, and they exhibited excellent antibacterial activity. Resin containing 15 % s-HAFs@EM exhibited the best flexural strength (118.67 ± 15.71 MPa) and elastic modulus (2.02 ± 0.30 GPa) (P < 0.05), which were increased by 65.43 % and 90.7 %, compared to those of neat resin, respectively. Resin with 15-20 % s-HAFs@EM showed high antibacterial rate (>85 %) when compared control group (P < 0.05). Furthermore, resin also exhibited a definite remineralization capability and good biosafety in vitro. SIGNIFICANCE: This novel multifunctional resin with improved mechanical property, desirable antibacterial activity and remineralization capability is promising to combat secondary caries.

Synthesis and Characterization of a Liquid Crystal-Modified Polydimethylsiloxane Rubber with Mechanical Adaptability Based on Chain Extension in the Process of Crosslinking.

The mechanical adaptive material is a kind of functional material that can effectively dissipate energy and suppress the increase of its stress under continuous strain in a large deformation area, which are vital in artificial muscles, connection devices, soft artificial intelligence robots, and other areas. Scientists have been working to broaden the platform of the material's mechanical adaptive platform and improve its mechanical strength by specific structure design. Based on it, we expect to introduce a mechanism of energy dissipation from the molecular chain scale to further improve mechanical adaptability. We developed a liquid crystal-modified polydimethylsiloxane rubber with mechanical adaptability based on chain extension in the process of crosslinking. Results showed that liquid crystal (0.7 mol %)-modified silicone rubber can obviously dissipate energy to achieve mechanical adaptive function, and the energy dissipation ratio of polydimethylsiloxane rubber (MQ), 4-propyl-4'-vinyl-1,1'-bi(cyclohexane)-modified polydimethylsiloxane rubber (3CCV-MQ), and 4-methoxyphenyl-4-(3-butenyloxy) benzoate-modified polydimethylsiloxane rubber (MBB-MQ) gradually decreases from 30 to 24%. Excessive thiol groups of liquid crystal-modified polydimethylsiloxane react with its vinyl group to achieve the chain extension, which significantly improves the mechanical strength from 2.74 to 5.83 MPa and elongation at break from 733 to 1096%. This research offers some new insights into improving the mechanical strength of silicone rubber and is of great significance for the application of the mechanical adaptive material.

Amide salt pyrolysis fabrication of graphene nanosheets with multi-excitation single color emission.

A novel and simple approach of using amide salt pyrolysis to produce photoluminescent (multi-excitation and single color emission) graphene nanosheets (GNs) with a thickness of <1 nm and a diameter of about 100-200 nm is described herein. It has characteristics of high water solubility, low toxicity, easy manufacturing, etc., and has potential application prospects in analytical chemistry and biomedicine.

Novel nanoparticle-modified multifunctional microcapsules with self-healing and antibacterial activities for dental applications.

OBJECTIVE: Although microcapsules (MCs) have been used for dental resins to achieve self-healing capabilities, the fragile organic shell and single healing event functions during the service period limit their use. Herein, a novel nanoparticle-modified MC with a nano-antibacterial inorganic filler (NIF) containing a quaternary ammonium salt was synthesized to address these issues. METHODS: MCs with 0 %-30 % NIFs were prepared via an in situ polymerization method and characterized their morphology, chemical composition, thermal stability, roughness, mechanical properties, and antibacterial effect. Subsequently, M-10 MCs were mixed into the resin matrix at a mass fraction of 7.5 %. The self-healing capability and cytotoxicity were evaluated. RESULTS: The introduction of nanomaterials enhances the shell of the MCs and endows them with an antibacterial effect. With the addition of NIFs, the roughness, modulus, and hardness values of MCs all increased (p < 0.05). The presence of M-10 MCs reduced the CFU by 2-3 orders of magnitude compared to the control group. The dental resin containing 7.5 % M-10 MCs obtained almost 69 % self-healing efficiency, without significantly compromising cell viability (p < 0.05). SIGNIFICANCE: Self-healing MCs with NIFs were prepared for the first time with strong antibacterial properties, a substantial self-healing capability, and low toxicity. This multifunctional MC is a promising candidate for use in dental resins to extend the service life and resolve the problem of bulk fracture and secondary caries.

Development of low-shrinkage dental adhesives via blending with spiroorthocarbonate expanding monomer and unsaturated epoxy resin monomer.

Polymerization shrinkage is one of the main drawbacks of dental resin adhesives. In this study, spiroorthocarbonate expanding monomer 3,9-diethyl-3,9-dimethylol -1,5,7,11-tetraoxaspiro-[5,5] undecane (DDTU) and unsaturated epoxy resin monomer Diallyl bisphenol A diglycidyl ether (DBDE) were synthesized and utilized as anti-shrinkage-coupling additive of methacrylate-based adhesives. Polymerization process and physicochemical properties including double bond conversion, polymerization shrinkage, compatibility, mechanical performance, thermal stability, contact angle, shear bond strength and cytotoxicity were characterized. Results indicated that adhesives containing anti-shrinkage-coupling additive had reduced volume shrinkage, improved compatibility and enhanced shear bond strength. When the amount of additive was 20 wt%, the volume shrinkage was decreased by 45.8% (4.17 ± 0.32%) and the shear bond strength was increased by 49.6% (19.64 ± 0.99 MPa). The results also showed that the use of additive had no adversely affect on double bond conversion and cytotoxicity. Therefore, novel low-shrinkage resin adhesives were prepared via blending with spiroorthocarbonate expanding monomer and unsaturated epoxy resin monomer.

The Effect of Phenyl Content on the Liquid Crystal-Based Organosilicone Elastomers with Mechanical Adaptability.

An elastomer with mechanical adaptability is a new kind of polymer material in which the increasing stress under continuous deformation is significantly inhibited in a large deformation area. Liquid crystal-based organosilicone elastomers, which can dissipate energy through reversible internal phase transition under external stimulation and have recoverable large deformation capacity, have drawn much interest as mechanical adaptability materials. However, there is no good way to control the mechanical adaptability at present. For this purpose, we prepared a new liquid crystal-based phenyl silicone rubber (LCMVPQ) using two-step click reactions and systematically explored the effect of phenyl content on its mechanical adaptability to achieve the regulation of mechanical adaptability. With an increase in phenyl content in the LCMVPQs, phenyl can hinder the rearrangement of the mesogenic units along the applied stress direction, which enables the adjustment of mechanical adaptability to meet the needs of different situations. In addition, the introduction of the liquid crystal phase impedes the internal friction of the molecular chain movement of the LCMVPQs and reduces the damping performance of silicone rubber. This research achieves the regulation of elastomers with mechanical adaptability and is expected to be applied in practical application fields.

Liquid Crystal-Based Organosilicone Elastomers with Supreme Mechanical Adaptability.

Elastomers with supreme mechanical adaptability where the increasing stress under continuous deformation is significantly inhibited within a large deformation zone, are highly desired in many areas, such as artificial muscles, flexible and wearable electronics, and soft artificial-intelligence robots. Such system comprises the advantages of recoverable elasticity and internal compensation to external mechanical work. To obtain elastomer with supreme mechanical adaptability, a novel liquid crystal-based organosilicon elastomer (LCMQ) is developed in this work, which takes the advantages of reversible strain-induced phase transition of liquid crystal units in polymer matrix and the recoverable nano-sized fillers. The former is responsible for the inhibition of stress increasing during deformation, where the external work is mostly compensated by internal phase transition, and the latter provides tunable and sufficient high tensile strength. Such LCMQs were synthesized with 4-methoxyphenyl 4-(but-3-en-1-yloxy)benzoate (MBB) grafted thiol silicone oil (crosslinker-g-MBB) as crosslinking agent, vinyl terminated polydimethylsiloxane as base adhesive, and fumed silica as reinforcing filler by two-step thiol-ene "click" reaction. The obtained tensile strength and the elongation at break are better than previously reported values. Moreover, the resulting liquid crystal elastomers exhibit different mechanical behavior from conventional silicone rubbers. When the liquid crystal content increases from 1% (w/w) to 4% (w/w), the stress plateau for mechanical adaptability becomes clearer. Moreover, the liquid crystal elastomer has no obvious deformation from 25 °C to 120 °C and is expected to be used in industrial applications. It also provides a new template for the modification of organosilicon elastomers.

Development of novel hydrophilic and antibacterial silicone rubber impression material for dental application.

OBJECTIVES: This investigation aimed to develop a novel hydrophilic and antibacterial silicone rubber impression material for dental application. METHODS: The basic formula of the new silicone rubber was determined on a preliminary study, and 6% polyether modified silicone oil was added as wetting agent to provide the hydrophilicity. No-vel nano-antibacterial inorganic fillers containing quaternary ammonium salt with long chain alkyl were incorporated into the hydrophilic silicone rubber impression materials at a mass fraction of 0%, 1%, 2%, 3%, 4%, or 5%. A commercial silicone rubber impression material was used as control. The mechanical properties, wettability, detail reproducibility, dimensional stability, and mixing time of silicone rubber materials were measured. Thin-film adhesion method and cell counting kit-8 method were used to detect the antibacterial property and cytotoxicity. Scanning electron microscopy (SEM) was chosen to observe the micromorphology of the novel silicone rubber. RESULTS: When the content of antibacterial filler exceeded 4%, the mechanical properties of the new silicone rubber decreased significantly (P<0.05). Compared with those of the control group, the contact angle and linear size change rate of different groups had no significant change at different time nodes, and the detail reproducibility was intact (P>0.05). The addition of antibacterial fillers had no significant effect on the mixing time (P>0.05). Adding 4% antibacterial fillers could result in the antibacterial rate of 95.26%, showing good antibacterial properties. No significant difference was found in the cytotoxicity of all groups (P>0.05). The SEM pictures of the cross section of the silicone rubber sample showed that the fillers had good compatibility with the silicone rubber matrix and distributed in the matrix evenly. CONCLUSIONS: A novel silicone rubber impression material containing 6% polyether modified silicone oil could obtain promising hydrophilic and antibacterial properties after being added with 4% antibacterial inorganic fillers.

Construction of Self-Healing Disulfide-Linked Silicone Elastomers by Thiol Oxidation Coupling Reaction.

Developing self-healing silicone elastomers are highly significant because of their promising applications. Herein, we present novel self-healing disulfide-linked silicone elastomers (SEs) based on thiol-terminated sulfur-containing heterochain polysiloxanes (P-SHs) and three thiol-containing crosslinkers, including pentaerythritol tetrakis(ß-mercaptopropionate) (PETMP), octa(3-mercaptopropyl)silsesquioxane (POSS-SH), and poly[(mercaptopropyl)methylsiloxane] (PMMS), via the thiol oxidation coupling reactions. The construction of these SEs can rapidly proceed at room temperature. The effects of crosslinker species and amounts on the formability and mechanical properties were investigated. The silicone elastomers can be self-healed by heating at 150 °C for 2 h or under UV radiation for 30 min after cutting them into pieces and the self-healing efficiency is >70%. Moreover, they can be utilized as adhesives for bonding glass sheets, which can hold a 200 g weight. The bonding is reversible and can repeatedly proceed many times, indicating that these materials can promisingly be applied as reversible adhesives. These results indicate that a thiol oxidation coupling reaction is a simple and effective strategy for the construction of self-healing disulfide-linked elastomers. Under this strategy, more disulfide-linked organic elastomers with self-healing properties can be designed and constructed and their applications can be further explored.

The bright fluorescence of non-aromatic molecules in aqueous solution originates from pH-induced CTE behavior.

Non-aromatic fluorescent materials with inherent visible light emission have received widespread attention. In this work, a biomimetic fluorescent molecule CA-AEP with a dipeptide structure is introduced. CA-AEP will emit bright biomimetic fluorescence in aqueous solutions by adjusting the pH, which has never been reported. This unique luminescent characteristic can be rationalized by the clustering-triggered emission (CTE) mechanism. In addition, CA-AEP can be used to monitor the maximum dynamic pH in the alkaline range of aqueous systems. Finally, the cytotoxicity assay to A549 cells showed that CA-AEP was non-toxic. Therefore, this work provides a new type of luminogen, which has potential application prospects in the field of environmental monitoring and cell biology.

Review on Development and Dental Applications of Polyetheretherketone-Based Biomaterials and Restorations.

Polyetheretherketone (PEEK) is an important high-performance thermoplastic. Its excellent strength, stiffness, toughness, fatigue resistance, biocompatibility, chemical stability and radiolucency have made PEEK attractive in dental and orthopedic applications. However, PEEK has an inherently hydrophobic and chemically inert surface, which has restricted its widespread use in clinical applications, especially in bonding with dental resin composites. Cutting edge research on novel methods to improve PEEK applications in dentistry, including oral implant, prosthodontics and orthodontics, is reviewed in this article. In addition, this article also discusses innovative surface modifications of PEEK, which are a focus area of active investigations. Furthermore, this article also discusses the necessary future studies and clinical trials for the use of PEEK in the human oral environment to investigate its feasibility and long-term performance.

Effects of air-abrasion pressure on mechanical and bonding properties of translucent zirconia.

OBJECTIVES: The purpose of this in vitro study was to investigate the effects of different air-abrasion pressures on flexural strength and shear bond strength of a translucent zirconia. MATERIALS AND METHODS: The translucent zirconia surface was treated with 50 µm abrasive alumina particles at different pressure: 0.1 MPa; 0.2 MPa; 0.3 MPa; 0.4 MPa; 0.5 MPa; untreated specimens were used as control group (n = 33). For each group, three-point bending test was used to evaluate the flexural strength, and surface characterizations were analyzed. Following adhesive bonding and water storage for 24 h, specimens were subdivided into groups baseline and aged (5000 thermocycles). Then, shear bond strength was measured and failure mode was recorded. Statistical analysis was performed with one-way ANOVA and Tukey test (α = 0.05). RESULTS: Increasing air-abrasion pressure (0.3 MPa, 0.4 MPa, and 0.5 MPa) decreased the flexural strength. Higher air-abrasion pressure resulted in rougher zirconia surfaces and caused more microcracks. The highest shear bond strength was obtained for zirconia surfaces abraded at 0.2 MPa (15.88 ± 2.70 MPa) and 0.3 MPa (14.32 ± 1.12 MPa). Aging did not decrease the strength for all groups except control group (p < 0.001). CONCLUSIONS: Air-abrasion with 50 µm abrasive alumina particles at 0.2 MPa could achieve good strength for translucent zirconia ceramics while maintaining adequate and durable bonding with resin cement. CLINICAL RELEVANCE: A total of 0.2 MPa is recommended for air-abrasion procedure applied before a dental restoration fabricated with translucent zirconia is bonded to resin cement.

[Development of novel self-adhesive resin cement with antibacterial and self-healing properties].

OBJECTIVE: This study aimed to develop novel self-adhesive resin cement with antibacterial and self-healing properties. Furthermore, the dentin bonding strength, mechanical properties, self-healing efficiency, and antibacterial property of the developed cement were measured. METHODS: Novel nano-antibacterial inorganic fillers that contain quaternary ammonium salts with long-chain alkyls were synthesized. These fillers were added into self-adhesive resin cement containing self-healing microcapsules at mass fractions of 0, 2.5%, 5.0%, 7.5%, or 10.0%. The dentin shear bonding test was used to test the bonding strength, whereas the flexural test was used to measure the flexural strength and elastic modulus of the cement. The single-edge V-notched beam method was used to measure self-healing efficiency, and human dental plaque microcosm biofilms were chosen to calculate the antibacterial property. RESULTS: The dentin shear bond strength significantly decreased when the mass fraction of the nano-antibacterial inorganic fillers in the novel cement reached 7.5% (P<0.05). The incorporation of 0, 2.5%, 5.0%, 7.5%, or 10.0% mass fraction of nano-antibacterial inorganic fillers did not adversely affect the flexural strength, elastic modulus, fracture toughness, and self-healing efficiency of the cement (P>0.1). Resin cement containing 2.5% mass fraction or more nano-antibacterial inorganic fillers significantly inhibited the metabolic activity of dental plaque microcosm biofilms, indicating strong antibacterial potency (P<0.05). CONCLUSIONS: The novel self-adhesive resin cement exhibited promising antibacterial and self-healing properties, which enable the cement to be used for dental applications.

[Application and potential future directions of self-healing polymers in dentistry].

Self-healing materials have rapidly developed in recent years to overcome the micro-cracks occurring in the polymer matrix. Self-healing ability offers autonomous crack repairs to prolong the service lives of polymers or polymer composites. As a main approach, extrinsic self-healing materials based on microcapsules have been applied in dentistry recently. This paper comprehensively presented and reviewed the definition and classification of self-healing materials, the synthesis of microcapsules, the calculation of self-healing efficiency, and the application of self-healing materials in dentistry. The future directions of self-healing polymers are also discussed.

Molecular Insights into Sequence Distributions and Conformation-Dependent Properties of High-Phenyl Polysiloxanes.

The excellent performance and wide applications of phenyl polysiloxanes are largely due to their phenyl units and monomer sequences. However, the relationship between molecular structure and material properties has not been explicitly elucidated. In this work, the sequence distribution and microstructure of random copolymers were quantitatively investigated by means of a molecular dynamics (MD) simulation combined with experimental verification. The results of 29Si NMR showed that the large number of phenyl units not only shortened the length of the dimethyl units, but also significantly increased the proportion of consecutive phenyl units. The simulation results indicated the attraction between adjacent phenyl groups that were effectively strengthened intra- and inter- molecular interactions, which determined the equilibrium population of conformations and the dynamics of conformational transitions. Furthermore, the evolution of bond angle distribution, torsion distribution, and mean-squared displacements (MSD) shed light on the conformational characteristics that induce the unique thermodynamics properties and photophysical behavior of high-phenyl polysiloxanes. Differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), spectrofluorimetry, and laser scanning confocal microscopy (LSCM) were performed to verify the conclusions drawn from the simulation. Overall, the complementary use of MD simulations and experiments provided a deep molecular insight into structure-property relationships, which will provide theoretical guidance for the rational design and preparation of high-performance siloxanes.