Multiple myeloma presenting with amyloid arthropathy as the first manifestation: Two case reports.

BACKGROUND: Multiple myeloma (MM) can be accompanied by amyloidosis, which occurs in a small number of patients and is characterized by deposition of light chains in the joints, leading to multiple myeloma-associated amyloid arthropathy (MAA). As a rare complication of MM, clinical manifestations of MAA are often similar to those of rheumatoid arthritis, and the two are easily confused. CASE SUMMARY: In recent years, our center treated two patients of MM with amyloid arthropathy as the first manifestation, both of whom presented with polyarthritis. After treatment for MM, both patients achieved complete remission. However, subsequently, the two patients underwent hip arthroplasty for femoral neck fractures. Congo red staining and immunofluorescence of the joint tissues confirmed MAA after surgery. Eventually, one of the patients died of MM recurrence, while the other survived. CONCLUSION: MAA should be regarded as an initial symptom of MM and should be taken seriously.

Anthraquinone Derivatives from a Marine-Derived Fungus Sporendonema casei HDN16-802.

Five new anthraquinone derivatives, auxarthrols D-H (1-5), along with two known analogues (6-7), were obtained from the culture of the marine-derived fungus Sporendonema casei. Their structures, including absolute configurations, were established on the basis of NMR, HRESIMS, and circular dichroism (CD) spectroscopic techniques. Among them, compound 4 represents the second isolated anthraquinone derivative with a chlorine atom, which, with compound 6, are the first reported anthraquinone derivatives with anticoagulant activity. Compounds 1 and 3 showed cytotoxic activities with IC50 values from 4.5 µM to 22.9 µM, while compounds 1, 3-4, and 6-7 showed promising antibacterial activities with MIC values from 12.5 µM to 200 µM. In addition, compound 7 was discovered to display potential antitubercular activity for the first time.

New Glutamine-Containing Azaphilone Alkaloids from Deep-Sea-Derived Fungus Chaetomium globosum HDN151398.

Three new azaphilone alkaloids containing glutamine residues, namely N-glutarylchaetoviridins A-C (1-3), together with two related compounds (4 and 5) were isolated from the extract of Chaetomium globosum HDN151398, a fungus isolated from a deep-sea sediment sample collected in South China Sea. Their structures were elucidated on the basis of extensive 1D and 2D NMR as well as HRESIMS spectroscopic data and chemical analysis. N-glutarylchaetoviridins A-C (1-3) represent the first class of chaetoviridins characterized by embedded glutamate residues. Amino acids incubation experiments produced five azaphilone laden different amino acids residues (6-10) which indicated that this method can enhanced the structural diversity of this strain by culturing with amino acids. Cytotoxicity of the isolated compounds were evaluated against a panel of human cancer cell lines.

[Curcumin Increases the Chemosensitivity of Multiple Myeloma to Bortezomib by Inhibiting the Notch1 Signaling Pathway].

OBJECTIVE: To evaluated the effect of curcumin on the bortezomib-resistant myeloma cells and the expression of Notch1 signaling pathway, in order to further explore its potential mechanism. METHODS: Curcumin, bortezomib, and curcumin combined bortezomib were added into RPMI 8266, U266, 5 nmol/L bortezomib-resistant RPMI 8266 (RPMI 8226-V5R), 5 nmol/L bortezomib-resistant U 266 (U266-V5R) and CD138+ plasma cells respectively. The cell proliferation was measured by MTT assay. the apoptotic rate was determined by flow cytometry, and the Western blot was used to detect the expression of apoptosis-related proteins. Then, the expression of Notch1 in cells was inhibited by notch1 inhibitor DAPT and RNA interference, the above-motioned experiments should be repeated. RESULTS: Compared with single drug-treated groups, the treatment with 2 drugs could further inhibit cell proliferation, induce apoptosis and enhance the inhibition effect on notch1 signaling pathway (P<0.05), while the inhibiting Notch1 signaling pathway could reduce cell proliferation and increase the expression of cleaved caspase-3. CONCLUSION: Curcumin can increase chemosensitivity of myeloma cells to bortezomib, this effect may be related to the inhibition of Notch1.

Peptide Mediated Antimicrobial Dental Adhesive System.

The most common cause for dental composite failures is secondary caries due to invasive bacterial colonization of the adhesive/dentin (a/d) interface. Innate material weakness often lead to an insufficient seal between the adhesive and dentin. Consequently, bacterial by-products invade the porous a/d interface leading to material degradation and dental caries. Current approaches to achieve antibacterial properties in these materials continue to raise concerns regarding hypersensitivity and antibiotic resistance. Herein, we have developed a multi-faceted, bio-functionalized approach to overcome the vulnerability of such interfaces. An antimicrobial adhesive formulation was designed using a combination of antimicrobial peptide and a ε-polylysine resin system. Effector molecules boasting innate immunity are brought together with a biopolymer offering a two-fold biomimetic design approach. The selection of ε-polylysine was inspired due to its non-toxic nature and common use as food preservative. Biomolecular characterization and functional activity of our engineered dental adhesive formulation were assessed and the combinatorial formulation demonstrated significant antimicrobial activity against Streptococcus mutans. Our antimicrobial peptide-hydrophilic adhesive hybrid system design offers advanced, biofunctional properties at the critical a/d interface.

New silyl-functionalized BisGMA provides autonomous strengthening without leaching for dental adhesives.

Resin-based composite has overtaken dental amalgam as the most popular material for direct restorative dentistry. In spite of this popularity the clinical lifetime of composite restorations is threatened by recurrent decay. Degradation of the adhesive leads to gaps at the composite/tooth interface-bacteria, bacterial by-products and fluids infiltrate the gaps leading to recurrent decay and composite restoration failure. The durability of resin-dentin bonds is a major problem. We address this problem by synthesizing silyl-functionalized BisGMA (e.g., silyl-BisGMA), formulating dental adhesives with the new monomer and determining the physicochemical properties and leaching characteristics of the silyl-BisGMA adhesives. Silyl-BisGMA was synthesized by stoichiometric amounts of BisGMA and 3-isocyanatopropyl trimethoxysilane (IPTMS). The control adhesive was a mixture based on HEMA/BisGMA (45/55, w/w). In the experimental formulations, BisGMA was partially or completely replaced by silyl-BisGMA. Water miscibility, polymerization behavior (Fourier transform infrared spectroscopy, FTIR), thermal property (modulated differential scanning calorimetry, MDSC), mechanical properties in dry and wet conditions (dynamic mechanical analysis, DMA), and leached species (HPLC) were investigated. Data from all tests were submitted to appropriate statistical analysis (α = 0.05). Silyl-BisGMA-containing adhesives exhibited comparable water miscibility, lower viscosities, and significantly improved degree of conversion of CC bond as compared to the control. After 4 weeks aqueous aging, the glass transition temperature and rubbery moduli of the experimental copolymers were significantly greater than the control (p < 0.05). HPLC results indicated a substantial reduction of leached HEMA (up to 99 wt%) and BisGMA (up to 90 wt%). By introducing silyl-functional group, the new BisGMA derivative exhibited potential as a monomer that can lead to dental adhesives with improved mechanical properties and reduced leaching under conditions relevant to the oral environment. STATEMENT OF SIGNIFICANCE: The low-viscosity adhesive that bonds the composite to the tooth (enamel and dentin) is intended to seal and stabilize the composite/tooth interface, but it degrades leading to a breach at the composite/tooth margin. As the most popular crosslinking monomer in adhesives, Bisphenol A-glycerolate dimethacrylate (BisGMA) has limitations, e.g. susceptible to hydrolysis and concomitant property degradation. A methoxysilyl-functionalized BisGMA derivative (silyl-BisGMA) was introduced in this work to respond to these limitations. Our results indicated that by introducing silyl-BisGMA, higher crosslinked networks were obtained without sacrificing the homogeneity, and the leached amount of HEMA was reduced up to 99%. This novel resin offers potential benefits including prolonging the functional lifetime of dental resin materials.

Modulating pH through lysine integrated dental adhesives.

OBJECTIVES: The objective of this study was to explore the effect of lysine integration to dental adhesives with respect to the polymerization kinetics, neutralization capacities in the acidic microenvironment, dynamic mechanical properties, and thermal properties. MATERIALS AND METHOD: Lysine was incorporated into liquid resin formulations at 2.5 and 5.0wt % with additional water/ethanol co-solvents. The co-monomer system contained 2-hydroxyethyl-methacrylate (HEMA) and Bisphenol A glycerolate dimethacrylate (BisGMA) with a mass ratio of 45/55. The kinetics of photopolymerization, neutralization capacities, lysine-leaching, dynamic mechanical properties and thermal properties of the control and experimental adhesives were analyzed. RESULTS: The degree of conversion of the experimental adhesive was increased substantially at 2.5wt% lysine as compared to the control. The experimental polymers provided acute neutralization of the acidic microenvironment. Approximately half of the lysine was released from the polymer network within one month. Under dry conditions and physiologic temperatures, the incorporation of lysine did not compromise the storage modulus. Comparison of the thermal properties suggests that the more compact structure of the control adhesive inhibits movement of the polymer chains resulting in increased Tg. SIGNIFICANCE: Incorporating lysine in the adhesive formulations led to promising results regarding modulating pH, which may serve as one aspect of a multi-spectrum approach for enhancing the durability of composite restorations. The results provide insight and lay a foundation for incorporating amino acids or peptides into adhesive formulations for pH modulation or desired bioactivity at the interfacial margin between the composite and tooth.

Fabrication of hybrid crosslinked network with buffering capabilities and autonomous strengthening characteristics for dental adhesives.

Ingress of bacteria and fluids at the interfacial gaps between the restorative composite biomaterial and the tooth structure contribute to recurrent decay and failure of the composite restoration. The inability of the material to increase the pH at the composite/tooth interface facilitates the outgrowth of bacteria. Neutralizing the microenvironment at the tooth/composite interface offers promise for reducing the damage provoked by cariogenic and aciduric bacteria. We address this problem by designing a dental adhesive composed of hybrid network to provide buffering and autonomous strengthening simultaneously. Two amino functional silanes, 2-hydroxy-3-morpholinopropyl (3-(triethoxysilyl)propyl) carbamate and 2-hydroxy-3-morpholinopropyl (3-(trimethoxysilyl)propyl) carbamate were synthesized and used as co-monomers. Combining free radical initiated polymerization (polymethacrylate-based network) and photoacid-induced sol-gel reaction (polysiloxane) results in the hybrid network formation. Resulting formulations were characterized with regard to real-time photo-polymerization, water sorption, leached species, neutralization, and mechanical properties. Results from real-time FTIR spectroscopic studies indicated that ethoxy was less reactive than methoxy substituent. The neutralization results demonstrated that the methoxy-containing adhesives have acute and delayed buffering capabilities. The mechanical properties of synthetic copolymers tested in dry conditions were improved via condensation reaction of the hydrolyzed organosilanes. The leaching from methoxy containing copolymers was significantly reduced. The sol-gel reaction provided a chronic and persistent reaction in wet condition-performance that offers potential for reducing secondary decay and increasing the functional lifetime of dental adhesives. STATEMENT OF SIGNIFICANCE: The interfacial gaps between the restorative composite biomaterial and the tooth structure contributes to recurrent decay and failure of the composite restoration. The inability of the material to increase the pH at the composite/tooth interface facilitates the outgrowth of more cariogenic and aciduric bacteria. This paper reports a novel, synthetic resin that provides buffering capability and autonomous strengthening characteristics. In this work, two amino functional silanes were synthesized and the effect of alkoxy substitutions on the photoacid-induced sol-gel reaction was investigated. We evaluated the neutralization capability (monitoring the pH of lactic acid solution) and the autonomous strengthening property (monitoring the mechanical properties of the hybrid copolymers under wet conditions and quantitatively analyzing the leachable species by HPLC). The novel resin investigated in this study offers the potential benefits of reducing the risk of recurrent decay and prolonging the functional lifetime of dental adhesives.

Probing the neutralization behavior of zwitterionic monomer-containing dental adhesive.

OBJECTIVE: To investigate the polymerization kinetics, neutralization behavior, and mechanical properties of amine-functionalized dental adhesive cured in the presence of zwitterionic monomer, methacryloyloxyethyl phosphorylcholine (MPC). METHODS: The control adhesive was a mixture based on HEMA/BisGMA/2-N-morpholinoethyl methacrylate (MEMA) (40/30/30, w/w/w). The control and experimental formulations containing MPC were characterized with regard to water miscibility of liquid resins, photopolymerization kinetics, water sorption and solubility, dynamic mechanical properties and leachables from the polymers (aged in ethanol). The neutralization behavior of the adhesives was determined by monitoring the pH of lactic acid (LA) solution. RESULTS: The water miscibility decreased with increasing MPC amount. The water sorption of experimental copolymer specimen was greater than the control. The addition of 8wt% water led to improved photo-polymerization efficiency for experimental formulations at MPC of 2.5 and 5wt%, and significant reduction in the cumulative amounts of leached HEMA, BisGMA, and MEMA, i.e. 90, 60 and 50% reduction, respectively. The neutralization rate of MPC-containing adhesive was faster than control. The optimal MPC concentration in the formulations was 5wt%. SIGNIFICANCE: Incompatibility between MEMA and MPC led to a decrease in water miscibility of the liquid resins. Water (at 8wt%) in the MPC-containing formulations (2.5-5wt% MPC) led to higher DC, faster RPmax and significant reduction in leached HEMA, BisGMA, and MEMA. The neutralization rate was enhanced with the addition of MPC in the amine-containing formulation. Promoting the neutralization capability of dentin adhesives could play an important role in reducing recurrent decay at the composite/tooth interface.

Characteristic analysis of aggressive non-Hodgkin's lymphoma complicated by autoim-mune hemolytic anemia / 中国肿瘤临床

Objective:To explore the clinical characteristics and laboratory data of aggressive non-Hodgkin's lymphoma(NHL)compli-cated by autoimmune hemolytic anemia(AIHA).Methods:Data of six patients with aggressive NHL complicated by AIHA treated at the Second Affiliated Hospital of Suzhou University between September 2013 and July 2016 were reviewed retrospectively. The onset symptoms,disease progression,therapy,and prognostic factors were analyzed.Results:From September 2013 to July 2016,155 pa-tients with aggressive NHL were treated in our hospital.Six of them were complicated by AIHA(3.9%),with three males and three fe-males,aged from 62 to 74.The median age was 67 years.The first clinical symptoms included the following:five presented with lymph-adenectasis,three had fever,and one presented with multiple bone destruction and bone pain,all complicated by progressive hemo-globin decrease.Histological examination of the six patients revealed three cases with diffuse large B-cell lymphoma(DLBCL),including one case with positive Bcl-2,Bcl-6,and C-myc,and one case with positive CD5;one case was peripheral T-cell lymphoma-not other-wise specified(PTCL-NOS);and two cases with angioimmunoblastic T-cell lymphoma(AITCL).Epstein-Barr virus(EBV)-mRNA(EBER) was detected by chromogenic in situ hybridization(CISH).Up to 100%(5/5)cases were EBER-positive.Eastern Cooperative Oncology Group scores of the six patients were three to four.All six cases were in the Ann-Arbor stagesⅢ-Ⅳand International Prognostic Index score 4-5.All cases belonged to the high risk group.At the time when lymphoma was confirmed by pathology,the median level of he-moglobin was 56(34-79)g/L.The median ratio of reticulocytes was 6.7(0.2-21.0)%.The positive rate of Coombs test was 100%.All cas-es showed autoantibodies against C3(1:64-1:2 048).Four cases showed antoantibodies against G antigen(±~1:16).The plasma con-centration of EBV DNA of three patients was detected and all increased.Except that 1 case gave up treatment,five patients received the chemotherapy with CHOP or R-CHOP.Four patients received prednisone between chemotherapy intermittent period.Two cases showed sustained complete response(CR).The overall survival(OS)was 20 and 14 months.Another patient with DLBCL and one pa-tient with PTCL-NOS died from secondary severe pulmonary infection and heart failure during the myelosuppression.The OS times were 1.5 and 2 months,respectively.One patient with AITCL died in the disease progression after four cycles of chemotherapy.The OS was 4.5 months.Conclusion:Aggressive NHL complicated by AIHA is common in older patients with poor prognosis.The incidence rate of EBV infection was high,and hemolysis is rapid and serious.The patients'tolerance to chemotherapy was poor.Early diagnosis and effective chemotherapy may improve patients'prognosis.

Characteristic analysis of aggressive non-Hodgkin's lymphoma complicated by autoim-mune hemolytic anemia / 中国肿瘤临床

Objective:To explore the clinical characteristics and laboratory data of aggressive non-Hodgkin's lymphoma(NHL)compli-cated by autoimmune hemolytic anemia(AIHA).Methods:Data of six patients with aggressive NHL complicated by AIHA treated at the Second Affiliated Hospital of Suzhou University between September 2013 and July 2016 were reviewed retrospectively. The onset symptoms,disease progression,therapy,and prognostic factors were analyzed.Results:From September 2013 to July 2016,155 pa-tients with aggressive NHL were treated in our hospital.Six of them were complicated by AIHA(3.9%),with three males and three fe-males,aged from 62 to 74.The median age was 67 years.The first clinical symptoms included the following:five presented with lymph-adenectasis,three had fever,and one presented with multiple bone destruction and bone pain,all complicated by progressive hemo-globin decrease.Histological examination of the six patients revealed three cases with diffuse large B-cell lymphoma(DLBCL),including one case with positive Bcl-2,Bcl-6,and C-myc,and one case with positive CD5;one case was peripheral T-cell lymphoma-not other-wise specified(PTCL-NOS);and two cases with angioimmunoblastic T-cell lymphoma(AITCL).Epstein-Barr virus(EBV)-mRNA(EBER) was detected by chromogenic in situ hybridization(CISH).Up to 100%(5/5)cases were EBER-positive.Eastern Cooperative Oncology Group scores of the six patients were three to four.All six cases were in the Ann-Arbor stagesⅢ-Ⅳand International Prognostic Index score 4-5.All cases belonged to the high risk group.At the time when lymphoma was confirmed by pathology,the median level of he-moglobin was 56(34-79)g/L.The median ratio of reticulocytes was 6.7(0.2-21.0)%.The positive rate of Coombs test was 100%.All cas-es showed autoantibodies against C3(1:64-1:2 048).Four cases showed antoantibodies against G antigen(±~1:16).The plasma con-centration of EBV DNA of three patients was detected and all increased.Except that 1 case gave up treatment,five patients received the chemotherapy with CHOP or R-CHOP.Four patients received prednisone between chemotherapy intermittent period.Two cases showed sustained complete response(CR).The overall survival(OS)was 20 and 14 months.Another patient with DLBCL and one pa-tient with PTCL-NOS died from secondary severe pulmonary infection and heart failure during the myelosuppression.The OS times were 1.5 and 2 months,respectively.One patient with AITCL died in the disease progression after four cycles of chemotherapy.The OS was 4.5 months.Conclusion:Aggressive NHL complicated by AIHA is common in older patients with poor prognosis.The incidence rate of EBV infection was high,and hemolysis is rapid and serious.The patients'tolerance to chemotherapy was poor.Early diagnosis and effective chemotherapy may improve patients'prognosis.

Self-Strengthening Hybrid Dental Adhesive via Visible-light Irradiation Triple Polymerization.

A self-strengthening methacrylate-based dental adhesive system was developed by introducing an epoxy cyclohexyl trimethoxysilane (TS) which contains both epoxy and methoxysilyl functional groups. The experimental formulation, HEMA/BisGMA/TS (22.5/27.5/50, wt%), was polymerized by visible-light. Real-time Fourier transform infrared spectroscopy (FTIR) was used to investigate in situ the free radical polymerization of methacrylate, ring-opening cationic polymerization of epoxy, and photoacid-induced sol-gel reactions. Among the three simultaneous reactions, the reaction rate of the free radical polymerization was the highest and the hydrolysis/condensation rate was the lowest. With 40s-irradiation, the degrees of conversion of the double bond and epoxy groups at 600 s were 73.2±1.2%, 87.9±2.4%, respectively. Hydrolysis of the methoxysilyl group was initially <5%, and increased gradually to about 50% after 48 h dark storage. Photoacids generated through the visible-light-induced reaction were effective in catalyzing both epoxy ring-opening polymerization and methoxysilyl sol-gel reaction. The mechanical properties of copolymers made with TS concentrations from 5 to 35 wt% were obtained using dynamic mechanical analysis (DMA). In wet conditions, the storage moduli at 70 °C and glass transition temperature were significantly higher than that of the control (p<0.05); these properties increased with TS concentration and storage time. The post reaction of hydrolysis/condensation of alkoxysilane could provide persistent strengthening whether in a neutral or acidic environment and these characteristics could lead to enhanced mechanical properties in the oral environment. The cumulative amount of leached species decreased significantly in the TS-containing copolymers. These results provide valuable information for the development of dental adhesives with reduced leaching of methacrylate monomers and enhanced mechanical properties under the wet, oral environment.

Effect of Partition of Photo-initiator Components and Addition of Iodonium Salt on the Photopolymerization of Phase-Separated Dental Adhesive.

The polymerization kinetics of physically separated hydrophobic- and hydrophilic-rich phases of a model dental adhesive have been investigated. The two phases were prepared from neat resin containing 2-hydroxyethyl methacrylate (HEMA) and bisphenol A glycerolate dimethacrylate (BisGMA) in the ratio of 45:55 (wt/wt). Neat resins containing various combinations of popular photo-initiating compounds, e.g., camphoquinone (CQ), ethyl 4-(dimethylamino)benzoate (EDMAB), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and diphenyliodonium hexafluorophosphate (DPIHP) were prepared. To obtain the two phases 33 wt% of deuterium oxide (D2O) was added to the neat resins. This amount of D2O exceeded the miscibility limit for the resins. The concentration of each component of the photo-initiating system in the two phases was quantified by HPLC. When combined with CQ, DMAEMA is less efficient as a co-initiator compared to EDMAB. The addition of DPIHP as the third component into either CQ/EDMAB or CQ/DMAEMA photo-initiating systems leads to comparable performance in both the hydrophobic- and hydrophilic-rich phases. The addition of the iodonium salt significantly improved the photopolymerization of the hydrophilic-rich phase; the hydrophilic-rich phase exhibited extremely poor polymerization when the iodonium salt was not included in the formulation. The partition concentration of EDMAB in the hydrophilic-rich phase was significantly lower than that of DMAEMA or DPIHP. This study indicates the need for a combination of hydrophobic/hydrophilic photosensitizer and addition of iodonium salt to improve polymerization within the hydrophilic-rich phase of the dental adhesive.

Mimicking nature: Self-strengthening properties in a dental adhesive.

Chemical and enzymatic hydrolysis provoke a cascade of events that undermine methacrylate-based adhesives and the bond formed at the tooth/composite interface. Infiltration of noxious agents, e.g. enzymes, bacteria, and so forth, into the spaces created by the defective bond will ultimately lead to failure of the composite restoration. This paper reports a novel, synthetic resin that provides enhanced hydrolytic stability as a result of intrinsic reinforcement of the polymer network. The behavior of this novel resin, which contains γ-methacryloxyproyl trimethoxysilane (MPS) as its Si-based compound, is reminiscent of self-strengthening properties found in nature. The efforts in this paper are focused on two essential aspects: the visible-light irradiation induced (photoacid-induced) sol-gel reaction and the mechanism leading to intrinsic self-strengthening. The FTIR band at 2840cm(-1) corresponding to CH3 symmetric stretch in -Si-O-CH3 was used to evaluate the sol-gel reaction. Results from the real-time FTIR indicated that the newly developed resin showed a limited sol-gel reaction (<5%) during visible-light irradiation, but after 48h dark storage, the reaction was over 65%. The condensation of methoxysilane mainly occurred under wet conditions. The storage moduli and glass transition temperature of the copolymers increased in wet conditions with the increasing MPS content. The cumulative amounts of leached species decreased significantly when the MPS-containing adhesive was used. The results suggest that the polymethacrylate-based network, which formed first as a result of free radical initiated polymerization, retarded the photoacid-induced sol-gel reaction. The sol-gel reaction provided a persistent, intrinsic reinforcement of the polymer network in both neutral and acidic conditions. This behavior led to enhanced mechanical properties of the dental adhesives under conditions that simulate the wet, oral environment. STATEMENT OF SIGNIFICANCE: A self-strengthening dental adhesive system was developed through a dual curing process, which involves the free radical photopolymerization followed by slow hydrolysis and condensation (photoacid-induced sol-gel reaction) of alkoxylsilane groups. The concept of "living" photoacid-induced sol-gel reaction with visible-light irradiation was confirmed in the polymer. The sol-gel reaction was retarded by the polymethacrylate network, which was generated first; the network extended the life and retained the activity of silanol groups. The self-strengthening behavior was evaluated by monitoring the mechanical properties of the hybrid copolymers under wet conditions. The present research demonstrates the sol-gel reaction in highly crosslinked network as a potentially powerful strategy to prolong the functional lifetime of engineered biomaterials in wet environments.

Probing the dual function of a novel tertiary amine compound in dentin adhesive formulations.

OBJECTIVES: A novel tertiary amine compound containing three methacrylate-urethane groups was synthesized for application in dentin adhesives. The synthesis, photopolymerization kinetics, and leaching were examined in an earlier study using this novel compound as the co-initiator (0.5 and 1.75wt% based on the total resin mass). The objective of this work was to investigate the potential of TUMA (8-(2-(((2-(methacryloyloxy)ethyl)carbamoyl)oxy)propyl)-6,10-dimethyl-4,12-dioxo-5,11-dioxa-3,8,13-triazapentadecane-1,15-diyl bis(2-methylacrylate)) to serve simultaneously as a co-initiator and co-monomer (15-45wt% based on the total resin mass) in dentin adhesive formulations. The polymerization kinetics, water sorption and dynamic mechanical properties of these novel formulations were determined. MATERIALS AND METHOD: The monomer system contained Bisphenol A glycerolate dimethacrylate (BisGMA), 2-hydroxyethylmethacrylate (HEMA) and TUMA (synthesized in our lab) at the mass ratio of 45/(55-x)/x. Two photoinitiator (PI) systems were compared. One initiator system contains three components: camphorquinone (CQ), diphenyliodonium hexafluorophosphate (DPIHP) and ethyl-4-(dimethylamino) benzoate (EDMAB) and the second initiator system contains CQ and DPIHP. The control adhesive formulations are: C0-3: HEMA/BisGMA 45/55 (w/w) and 3-component PI and C0-2: HEMA/BisGMA 45/55 (w/w) and 2-component PI. These controls were used as a comparison to the experimental adhesive resins (Ex-3 or Ex-2), in which x represents the weight percentage of synthesized co-monomer (TUMA) to replace part of BisGMA. The control and experimental adhesive formulations were photo-polymerized and compared with regard to the degree of conversion (DC), polymerization rate (Rp), water sorption and dynamic mechanical analysis (DMA) under both dry and wet conditions. RESULTS: C0-3 and Ex-3 formulations had similar DC, while the DC of Ex-2 formulation was higher than C0-2. The DC was similar when comparing the two- component with the three-component photoinitiator system when TUMA was used at the same concentration. DMA under dry conditions shows higher rubbery storage modulus for all experimental formulations, while storage modulus at rubbery region under wet conditions was decreased as compared with control (C0-3). There was no statistically significant difference for the DMA results under both dry and wet conditions when comparing two- and three-component initiator systems with the same TUMA concentration. SIGNIFICANCE: The newly synthesized TUMA could serve simultaneously as a co-monomer and co-initiator in the absence of commercial co-initiator. This study provides information for the future development of new co-monomer/co-initiator for dentin adhesives and dental composites.

Tris(trimethylsilyl)silane as a co-initiator for dental adhesive: Photo-polymerization kinetics and dynamic mechanical property.

OBJECTIVES: The purpose of this study was to evaluate the polymerization behavior of a model dentin adhesive with tris(trimethylsilyl)silane (TTMSS) as a co-initiator, and to investigate the polymerization kinetics and mechanical properties of copolymers in dry and wet conditions. METHODS: A co-monomer mixture based on HEMA/BisGMA (45/55, w/w) was used as a model dentin adhesive. The photoinitiator system included camphorquinone (CQ) as the photosensitizer and the co-initiator was ethyl-4-(dimethylamino) benzoate (EDMAB) or TTMSS. Iodonium salt, diphenyliodonium hexafluorophosphate (DPIHP) serving as a catalyst, was selectively added into the adhesive formulations. The control and the experimental formulations were characterized with regard to the degree of conversion (DC) and dynamic mechanical properties under dry and wet conditions. RESULTS: In two-component photoinitiator system (CQ/TTMSS), with an increase of TTMSS concentration, the polymerization rate and DC of CC double bond increased, and showed a dependence on the irradiation time and curing light intensity. The copolymers that contained the three-component photoinitiator system (CQ/TTMSS/DPIHP) showed similar dynamic mechanical properties, under both dry and wet conditions, to the EDMAB-containing system. SIGNIFICANCE: The DC of formulations using TTMSS as co-initiator showed a strong dependence on irradiation time. With the addition of TTMSS, the maximum polymerization rate can be adjusted and the network structure became more homogenous. The results indicated that the TTMSS could be used as a substitute for amine-type co-initiator in visible-light induced free radical polymerization of methacrylate-based dentin adhesives.

Development of methacrylate/silorane hybrid monomer system: Relationship between photopolymerization behavior and dynamic mechanical properties.

Resin chemistries for dental composite are evolving as noted by the introduction of silorane-based composites in 2007. This shift in the landscape from methacrylate-based composites has fueled the quest for versatile methacrylate-silorane adhesives. The objective of this study was to evaluate the polymerization behavior and structure/property relationships of methacrylate-silorane hybrid systems. Amine compound ethyl-4-(dimethylamino) benzoate (EDMAB) or silane compound tris(trimethylsilyl) silane (TTMSS) was selected as coinitiators. The mechanical properties of the copolymer were improved significantly at low concentrations (15, 25, or 35 wt %) of silorane when EDMAB was used as coinitiator. The rubbery moduli of these experimental copolymers were increased by up to 260%, compared with that of the control (30.8 ± 1.9 MPa). Visible phase separation appeared in these formulations if the silorane concentrations in the formulations were 50-75 wt %. The use of TTMSS as coinitiator decreased the phase separation, but there was a concomitant decrease in mechanical properties. In the neat methacrylate formulations, the maximum rates of free-radical polymerization with EDMAB or TTMSS were 0.28 or 0.06 s(-1) , respectively. In the neat silorane resin, the maximum rates of cationic ring-opening polymerization with EDMAB or TTMSS were 0.056 or 0.087 s(-1) , respectively. The phase separation phenomenon may be attributed to differences in the rates of free-radical polymerization of methacrylates and cationic ring-opening polymerization of silorane. In the hybrid systems, free-radical polymerization initiated with EDMAB led to higher crosslink density and better mechanical properties under dry/wet conditions. These beneficial effects were, however, associated with an increase in heterogeneity in the network structure. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 841-852, 2016.

The influence of water on visible-light initiated free-radical/cationic ring-opening hybrid polymerization of methacrylate/epoxy: Polymerization kinetics, crosslinking structure and dynamic mechanical properties.

The objective of this study was to determine the influence of water on the polymerization kinetics, crosslinking structure and dynamic mechanical properties of methacrylate/epoxy polymers cured by visible-light initiated free-radical/cationic ring-opening hybrid polymerization. Water-containing formulations were prepared by adding ~4-7 wt% D2O depending on the water miscibility of monomer resins. The water-containing adhesives were compared with the adhesives photo-cured in the absence of water. The results show an improved degree of conversion for both methacrylates and epoxy by adding water. The rate of the epoxy cationic ring-opening reaction is increased while the rate of free radical polymerization is decreased in the presence of water. The decreased crosslinking density noted in the presence of water suggests that the chain transfer reaction between water and epoxy competes with the hydroxyl-based chain transfer mechanism. There is potential application of this visible-light initiated hybrid polymerization in biomaterials, e.g. dental restorations and tissue engineering scaffolds.