Synthesis of star-shaped poly(lactide)s, poly(valerolactone)s and poly(caprolactone)s via ROP catalyzed by N-donor tin(ii) cations and comparison of their wetting properties with linear analogues.

In this study, we report the use of N-coordinated tin(ii) cations [L1→Sn(H2O)][OTf]2·THF (1) and [L1→SnCl][SnCl3] (2) (L1 = 1,2-(C5H4N-2-CH = N)2CH2CH2) as efficient ROP catalysts, which, in combination with benzyl alcohol, afford well-defined linear poly(ε-caprolactone) (PCL) and poly(δ-valerolactones) (PVL) via an activated monomer mechanism (AMM). Thanks to the versatility of complexes 1 and 2 as catalysts, star-shaped PCL, PVL and PLA were also prepared using three-, four-, five- and six-functional alcohols. The number of arms was determined by SEC-MALS-Visco analysis. Spin-coated thin layers of linear and selected six-armed polymers were further studied in terms of their wettability to water. Attention was focused on the influence of the composition and structure of the polymers. Finally, to increase the hydrophobic properties of the studied polymers, stannaboroxines L2(Ph)Sn[(OB-(C6H4-4-CF3))2O] and L2(Ph)Sn[(OB-(C6H4-3,5-CF3)2)2O] (L2 = C6H3-2,6-(Me2NCH2)2) were applied.

Bio-based unsaturated polyester resin from post-consumer PET.

This study explores the utilization of post-consumer poly(ethylene terephthalate) (PET) as a material in the synthesis of styrene-free unsaturated polyester (UP) resin. The process involves glycolysis of PET waste with diethylene glycol and condensation polymerization with bio-based itaconic acid. The resulting unsaturated polyester possesses reactive methylidene functions that, in contrast to commonly employed fumarates/maleates, facilitate copolymerization with non-styrene reactive diluents. To formulate the resins, methacrylates and itaconates were used for dilution, and the curing process is achieved through a redox initiation system at room temperature, followed by post-curing at elevated temperatures. The cured formulations were characterized by their glass transition temperature, determined by DMA analysis. Mechanical properties were evaluated using standardized tests in tension, flexure, and compression. Particularly promising characteristics are observed in formulations incorporating bio-based dimethyl itaconate (DMI), allowing the formulation of materials with a high ultimate flexural strength (σf,max = 161.4 MPa) and compressive yield point (σc,yield = 131.3 MPa). Furthermore, the low volatility of DMI addresses the health, safety, and ecological concerns associated with the commonly used styrene. This technology not only presents a promising avenue for sustainable UP resin for glass fiber reinforced composites but also allows upcycling PET waste.

Metal hypersensitivity and pro-inflammatory cytokine production in patients with failed orthopedic implants: A case-control study.

Orthopedic implants heal well without complications in most patients but fail for unclear reasons in some individuals. This study determined the relevance of metal hypersensitivity in patients with failed orthopedic implants and those requiring orthopedic implant surgery. The study included 35 patients with failed orthopedic implants and 15 subjects scheduled for orthopedic implant surgery. The production of selected pro-inflammatory cytokines was measured in patients with failed orthopedic implants. Metal hypersensitivity was measured in all subjects using the MELISA® test. Of common metals in orthopedic alloys, the patients with failed orthopedic implants responded most frequently to nickel, chromium, titanium, iron, and molybdenum. Hypersensitivity to metals found in implants was measured in 40% of patients with failed implants. The study also showed that titanium exposure in patients with titanium hypersensitivity might lead to implant failure. Metal hypersensitivity testing should be offered to patients before surgery to minimize the risk of implant failure.

Photobiomodulation Therapy After Mesiodens Surgery: Evaluation of Immunological Markers and Three-Dimensional X-Ray Analysis-Placebo-Controlled Study.

Objective: Photobiomodulation therapy (PBMT) applies therapeutic lasers or light-emitting diodes radiation to the surface of the body. From the medical point of view, PBMT systems have been employed for reducing pain, inflammation, and edema, promoting healing of wounds, deeper tissues and nerves, preventing tissue damage, etc. Background data: PBMT or biostimulation has a wide range of applications in maxillofacial surgery. It is known that the therapy effect using three-dimensional (3D) image was not really clear during the healing process. Materials and methods: The treatment group comprised 38 patients, 18 of them were treated with laser radiation (diode laser 808 nm) and 20 patients presented the control group. The surgery plan was monitored using cone beam computed tomography, in particular the number, shape, and size of mesiodens were registered. The effectivity of laser therapy was assessed based on immunological tests-secretory immunoglobulin A (sIgA) and lysozyme levels measured in nonstimulated saliva before and after treatment. Results: For sIgA (both in millimeters and milligrams per liter), the measurements displayed differences between pre- and postsurgery values, the postsurgery values being significantly lower than the presurgery values. In addition, interaction with the laser treatment plan was found, meaning that the laser treatment affected the sIgA levels. The decrease in sIgA levels in the control group was statistically significant. However, there was no significant change in sIgA levels in the laser group. The lysozyme trends appeared to be identical to the sIgA levels, that is, rising in the laser group and decreasing in the control group. The initial values for each group, however, go in the opposite direction. Conclusions: The study has shown that the 3D techniques and technologies in combination with therapeutic laser systems could support not only a treatment plan, but they also directly influence the process of healing and reduce inflammation. The study was carried out under clinical project No. 00064203 (FN MOTOL).

Modification of Poly(lactic acid) by the Plasticization for Application in the Packaging Industry.

Plastic products, especially in the packaging industry, have become the main commodities penetrating virtually every aspect of our lives. Unfortunately, their omnipresence is not neutral to the natural environment. Pollution in the form of microplastics is a global problem. Therefore, green technologies that enter into the circular economy become an important topic. As part of the research work, the modification of poly(lactic acid) has been studied for use in the packaging industry. Due to its intrinsic rigidity, plasticizing substances had to be introduced in PLA in order to improve its plastic deformability. Both high-molecular compounds such as ethoxylated lauryl alcohol, block copolymer of ethylene oxide and propylene oxide, and ethoxylated stearic acid as well as low-molecular compounds such as di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate, and triethyl citrate were used. The samples extruded from plasticized polymers were characterized using differential scanning calorimetry, thermal gravimetric analysis, and mechanical properties including Young's modulus. The melt flow rate (MFR) and molar mass distribution were determined. For all modified samples the glass transition temperature, depending on the plasticizer used, was shifted towards lower values compared to the base polymer. The best result was obtained for di-2-ethylhexyl adipate (ADO) and di-2-ethylhexyl sebacate (SDO). The elongation at break increased significantly for ADO at about 21%. The highest elongation was obtained for SDO (about 35%), although it obtained a higher glass temperature. The degradation of the polymer was not observed for both plasticizers. For these plasticizers (ADO and SDO) it also lowered Young's module by about 26%, and at the infrared spectrum deformation of peaks were observed, which may indicate the interaction of the ester carbonyl group of PLA with plasticizers. Therefore it can be concluded that they are good modifiers. The selected plasticizers that are used in the production of food contact materials, in particular in the production of PVC (polyvinyl chloride) food films, also exhibited great potential to be applied to PLA food films, and exhibit better properties than the citrate, which are indicated in many publications as PLA plasticizers.

N-Donor stabilized tin(II) cations as efficient ROP catalysts for the synthesis of linear and star-shaped PLAs via the activated monomer mechanism.

α-Iminopyridine ligands L1 (2-(CHN(C6H2-2,4,6-Ph3))C5H4N), L2 (2-(CHN(C6H2-2,4,6-tBu3))C5H4N) and L3 (1,2-(C5H4N-2-CHN)2CH2CH2) differing by the steric demand of the substituent on the imine CHN group and by the number of donating nitrogen atoms were utilized to initiate a Lewis base mediated ionization of SnCl2 in an effort to prepare ionic tin(II) species [L1-3 → SnCl][SnCl3]. The reaction of L1 and L2 with SnCl2 led to the formation of neutral adducts [L1 → SnCl2] (2) and [L2 → SnCl2] (3). The preparation of the desired ionic compounds was achieved by subsequent reactions of 2 and 3 with an equivalent of SnCl2 or GaCl3. In contrast, ligand L3 containing four donor nitrogen atoms showed the ability to ionize SnCl2 and also Sn(OTf)2, yielding [L3 → SnCl][SnCl3] (7) and [L3 → Sn(H2O)][OTf]2 (8). The study thus revealed that the reaction is dependent on the type of the ligand. The prepared complexes 4-8 together with the previously reported [{2-((CH3)CN(C6H3-2,6-iPr2))-6-CH3O-C5H3N}SnCl][SnCl3] (1) were tested as catalysts for the ROP of L-lactide, which could operate via an activated monomer mechanism. Finally, a DFT computational study was performed to evaluate the steric and electronic properties of the ionic tin(II) species 1 and 4-8 together with their ability to interact with the L-lactide monomer.

Titanium and Other Metal Hypersensitivity Diagnosed by MELISA® Test: Follow-Up Study.

This study is aimed at proving the clinical benefit of the MELISA® test in the minimization or complete elimination of health problems in patients with confirmed hypersensitivity to metals used for tissue replacements. A group of 305 patients aged 20-75 years with previously proven metal hypersensitivity (initial MELISA® test), mainly to titanium and then to another fifteen metals, was chosen from the database at the Institute of Dental Medicine. From these patients, a final group of 42 patients agreed to participate in the study, 35 of which were female and 7 were male. The patients completed a special questionnaire aimed at information regarding change of health status from their last visit and determining whether the results of the initial MELISA® test and recommendations based on it were beneficial for patients or not. They were clinically examined, and peripheral blood samples were taken to perform follow-up MELISA® tests. Questionnaire data was processed, and the follow-up MELISA® test results were compared with the results of the initial MELISA® tests. For statistical analysis, the Fisher's exact test and paired T-test were used. Thirty-two patients reported that they followed the recommendations based on the results of the initial MELISA® tests, and of these, 30 patients (94%) confirmed significant health improvement. Six patients did not follow the recommendation, and from these, only one patient reported an improvement in his health problems. By comparison of the initial and follow-up MELISA® test results, it can be stated that the hypersensitivity to the given metal decreased or disappeared after the therapeutic interventions performed based on the initial MELISA® test results. The evaluation of the data obtained from patients in this study confirmed a significant clinical benefit of MELISA® test.

R/G Value-A Numeric Index of Individual Periodontal Health and Oral Microbiome Dynamics.

The dysbiosis of oral microbiome (OM) precedes the clinical signs of periodontal disease. Its simple measure thus could indicate individuals at risk of periodontitis development; however, such a tool is still missing. Up to now, numerous microbial taxa were associated with periodontal health or periodontitis. The outputs of most studies could, nevertheless, be slightly biased from following two reasons: First, the healthy group is often characterized only by the absence of the disease, but the individuals could already suffer from dysbiosis without any visible signs. Second, the healthy/diseased OM characteristics are frequently determined based on average data obtained for whole groups of periodontally healthy persons versus patients. Especially in smaller sets of tested individuals the typical individual variability can thus complicate the unambiguous assignment of oral taxa to respective state of health. In this work the taxonomic composition of OM was evaluated for 20 periodontally healthy individuals and 15 patients with chronic periodontitis. The narrowed selection set of the most diseased patients (confirmed by clinical parameters) and the most distant group of healthy individuals with the lowest probability of dysbiosis was determined by clustering analysis and used for identification of marker taxa. Based on their representation in each individual oral cavity we proposed the numeric index of periodontal health called R/G value. Its diagnostic potential was further confirmed using independent set of 20 periodontally healthy individuals and 20 patients with periodontitis with 95 percent of samples assigned correctly. We also assessed the individual temporal OM dynamics in periodontal health and we compared it to periodontitis. We revealed that the taxonomic composition of the system changes dynamically but generally it ranges within values typical for periodontal health or transient state, but far from values typical for periodontitis. R/G value tool, formulated from individually evaluated data, allowed us to arrange individual OMs into a continuous series, instead of two distinct groups, thus mimicking the gradual transformation of a virtual person from periodontal health to disease. The application of R/G value index thus represents a very promising diagnostic tool for early prediction of persons at risk of developing periodontal disease.

Retention Mechanism of Branched Macromolecules in Size Exclusion Chromatography.

The theory of Stockmayer in the modifications of Thurmond and Zimm has been used for the description of the size exclusion chromatography separation of randomly branched molecules with tetrafunctional branch points. It is assumed that free chain ends, created by the branching process, cause the molecules to be entrapped in the pores of the column packing with the time of their release given by the exponential law characteristic for the monomolecular reactions. Using this assumption, the anomalous elution behavior of such molecules can be modeled. With increasing elution volume, the average values of radius of gyration and, to a lesser degree, of molecular weight decrease and, after passing a minimum, again increase in the low-molecular weight region.

Branched PLGA derivatives with tailored drug delivery properties.

Despite several shortcomings such as extreme hydrophobicity, low drug capacity, characteristic triphasic drug release pattern with a high burst effect, poly(lactic-co-glycolic acid derivatives are widely used in drug delivery. Most frequent attempts to improve their properties are blending with other polymers or synthesis of block copolymers. We introduce a new class of branched poly(lactic-co-glycolic acid) derivatives as promising biodegradable carriers for prolonged or targeted drug release systems, employed as thin adhesive films, solid dispersions, in situ forming implants or nanoparticles. A series of poly(lactic-co-glycolic acid) derivatives with lower molar mass and star or comb architecture were synthesized by a simple, catalyst free, direct melt polycondensation method not requiring purification of the obtained sterile product by precipitation. Branching monomers used were mannitol, pentaerythritol, dipentaerythritol, tripentaerythritol and polyacrylic acid. The products were characterized by molar mass averages, average branching ratio, rheological and thermal properties.

Side Effects of Dental Metal Implants: Impact on Human Health (Metal as a Risk Factor of Implantologic Treatment).

Dental implants are often made of titanium alloys. Implant therapy currently promises a good long-term result without impacting health; however, its success depends on many factors. In this article, the authors focus on the most common risk factors associated with metallic surgical implants. Titanium-induced hypersensitivity can lead to symptoms of implant rejection. Corrosion and biofilm formation are additional situations in which these symptoms may occur. For medical purposes, it is important to define and discuss the characteristics of metals used in implantable devices and to ensure their biocompatibility. To avoid hypersensitivity reactions to metallic dental implants, precautionary principles for primary prevention should be established.

Getting Closer to Absolute Molar Masses of Technical Lignins.

Determination of molecular weight parameters of native and, in particular, technical lignins are based on size exclusion chromatography (SEC) approaches. However, no matter which approach is used, either conventional SEC with a refractive index detector and calibration with standards or multi-angle light scattering (MALS) detection at 488 nm, 633 nm, 658 nm, or 690 nm, all variants can be severely erroneous. The lack of calibration standards with high structural similarity to lignin impairs the quality of the molar masses determined by conventional SEC, and the typical fluorescence of (technical) lignins renders the corresponding MALS data rather questionable. Application of MALS detection at 785 nm by using an infrared laser largely overcomes those problems and allows for a reliable and reproducible determination of the molar mass distributions of all types of lignins, which has been demonstrated in this study for various and structurally different analytes, such as kraft lignins, milled-wood lignin, lignosulfonates, and biorefinery lignins. The topics of calibration, lignin fluorescence, and lignin UV absorption in connection with MALS detection are critically discussed in detail, and a reliable protocol is presented. Correction factors based on MALS measurements have been determined for commercially available calibration standards, such as pullulan and polystyrene sulfonate, so that now more reliable mass data can be obtained also if no MALS system is available and these conventional calibration standards have to be resorted to.

Low-Level Laser Therapy After Wisdom Teeth Surgery: Evaluation of Immunologic Markers (Secretory Immunoglobulin A and Lysozyme Levels) and Thermographic Examination: Placebo Controlled Study.

OBJECTIVE: The goal of this investigation is to analyze the effect of therapeutic low-level laser therapy (LLLT) to have a possibility to check pain and inflammation connected with surgical removal of impacted lower third molars in general anesthesia or even phobia [not accompanied by pain or fear of dental treatment, using immunologic markers-secretory immunoglobulin A (sIgA) and lysozyme]. The healing process was also monitored by infrared thermography. BACKGROUND DATA: LLLT can accelerate the proliferation phase of healing and decrease the inflammatory reaction, but the effect is not really clear. MATERIALS AND METHODS: The treatment group comprised 213 impacted third molars (144 laser group and 74 placebo group). Laser radiation (diode laser 830 nm) was applied. The effectivity of laser therapy was evaluated based on immunological tests, that is, before and after treatment with sIgA and lysozyme in nonstimulated saliva. Thermographic examination was performed by infrared camera. RESULTS: After laser irradiation, the sIgA decreases from 546.91 mg/L (SD 354.58) to 304.91 mg/L (SD 191.96), and in the control group from 602.25 mg/L (SD 343.62) to 425.62 mg/L (SD 220.51); the differences were significant, the lysozyme value being lower. After laser therapy, the laser and placebo sides in the area of the third molars were differed in 0.2°C. CONCLUSIONS: The 830 nm wavelength penetrates to deep-seated tissues. A positive association was found between concentration of salivary sIgA and lysozyme in the saliva after LLLT application. The deep-seated wounds after wisdom teeth extraction had no effect on temperature rise in the face.

C-reactive protein in patients with aggressive periodontitis.

BACKGROUND/PURPOSE: The aim of this study was to evaluate and compare the systemic levels of C-reactive protein (CRP) in peripheral blood samples of patients with aggressive periodontitis during the first twelve months of periodontal treatment, at exactly six month interval measurements, and compare them with clinical periodontal parameters. MATERIALS AND METHODS: All patients (N = 45) were examined prior to the initiation of periodontal treatment. Patients were divided into two groups GAgP (Generalised form of aggressive periodontitis, N = 23) and group LAgP (Localised form of aggressive periodontitis, N = 22). Control group (CON) included 60 individuals with healthy periodontium. The levels of CRP were determined in both groups GAgP and LAgP three times in 6 month intervals during the periodontal treatment. RESULTS: CRP is a plasma protein that reflects the extent of the acute phase response to inflammation and is one of the markers of choice for monitoring this response. In our study, CRP levels decreased in course of periodontal treatment in both groups (GAgP and LAgP) in a similar way as bleeding on probing (BOP) and probing pocket depth (PPD) indices. CONCLUSION: Our study results showed that CRP levels, as well as bleeding on probing (BOP) and probing pocket depth (PPD), indices decreased in course of periodontal treatment in patients with generalised and localised aggressive periodontitis. Therefore this marker might be exploitable as a means to evaluate periodontal health in patients with aggressive periodontitis.

Salivary Markers for Periodontal and General Diseases.

The determination of biomarkers in saliva is becoming an important part of laboratory diagnostics and the prediction of not only periodontal, but also other tissue and organ diseases. Biomarkers in saliva (e.g., enzymes, protein markers, or oxidative stress markers) can be used for activity determination and for periodontal disease prognosis. Saliva also contains many markers which can predict the risk of certain diseases (e.g., diabetes mellitus, cardiovascular, oncology, endocrinology, and psychiatric diseases). The study of salivary components proteomics clearly shows the relationship of periodontal diseases and diseases of distant systems, organs, or tissues.

Periodontal Diseases and Dental Caries in Children with Type 1 Diabetes Mellitus.

Type 1 diabetes mellitus is a chronic metabolic disease of an autoimmune origin with early manifestation predominantly in the childhood. Its incidence has been rising in most European countries. Diabetes has been intensively studied by all branches of medicine. There were a number of studies investigating oral consequences of diabetes; however, unambiguous conclusions were drawn only for the relationship between diabetes and periodontal impairment. Many studies confirmed higher plaque levels and higher incidence of chronic gingivitis both in adults and in children with diabetes. Juvenile periodontitis is rare both in healthy subjects and in those with type 1 diabetes. Yet certain findings from well-conducted studies, for example, differences in oral microflora or the impact of metabolic control of diabetes on periodontal health, indicate a higher risk of periodontitis in children with type 1 diabetes. As for the association of diabetes and dental caries, the results of the studies are inconsistent. However, it was found that some risk factors for dental caries are either more or less prevalent in the diabetic population. Despite an extensive research in this area we have to acknowledge that many questions have remained unanswered. There is a need for continued, thorough research in this area.

C-Reactive Protein in Peripheral Blood of Patients with Chronic and Aggressive Periodontitis, Gingivitis, and Gingival Recessions.

CRP is a plasma protein that reflects a measure of the acute phase response to inflammation and is one of the markers of choice in monitoring this response. CRP can be used for the prediction and early detection of periodontal disease. The aim of this study was to compare and evaluate the systemic levels of CRP in the peripheral blood samples of patients with chronic and aggressive periodontitis, gingivitis, and gingival recessions and compare them with periodontal clinical parameters. All patients (N = 158) were examined prior to the initiation of periodontal treatment. Patients were divided into four groups. Group A consisted of 26 patients with aggressive periodontitis, Group B consisted of 111 patients with chronic periodontitis, Group C consisted of 13 patients with gingivitis, and Group D consisted of 8 patients with gingival recessions. Our study results indicate that CRP levels increase subsequently with the severity of the periodontal disease and that the bleeding on probing index showed much better positive correlation with the CRP levels compared to the pocket depth index in both periodontitis patients groups, especially in aggressive periodontitis patients.

The effect of IL-4 gene polymorphisms on cytokine production in patients with chronic periodontitis and in healthy controls.

Chronic periodontitis (CP) is an inflammatory disease of the teeth-supporting tissues in which genetic predisposition, dental plaque bacteria, and immune mechanisms all play important roles. The aim of this study was to evaluate the occurrence of IL-4 gene polymorphisms in chronic periodontitis and to investigate the association between polymorphisms and cytokines production after bacterial stimulation. Sixty-two subjects (47 CP patients and 15 healthy controls) with detected two polymorphisms in the IL-4 gene (-590C/T and intron 3 VNTR) were examined. Production of cytokines (IL-1α, IL-1ß, IL-4, IL-5, IL-6, IL-10, IL-17, TNFα, INFγ, and VEGF) was studied after in vitro stimulation of isolated peripheral blood by mitogens (Pokeweed mitogen, Concanavalin A), dental plaque bacteria (Aggregatibacter actinomycetemcomitans, Tannerella forsythia, Porphyromonas gingivalis, and Prevotella intermedia), and Heat Shock Protein (HSP) 70 by the Luminex multiplex cytokine analysis system. The results were correlated with IL-4 genotypes in patients with CP and healthy controls. The mononuclear cells isolated from peripheral blood of CP patients with selected IL-4 polymorphisms significantly altered the production of IFNγ, IL-10, IL-1ß, IL-1α, TNFα, and IL-6 after stimulation by HSP 70 or selected bacteria (from P < 0.001 to P < 0.05). IL-4 gene polymorphisms may influence the function of mononuclear cells to produce not only interleukin-4 but also other cytokines, especially in patients with CP.

Enhanced multiparametric hyaluronan degradation for production of molar-mass-defined fragments.

Hyaluronic acid (HA) is known to serve as a dynamic mediator intervening in many physiological functions. Its specific effect has been repeatedly confirmed to be strongly influenced by the molecular size of hyaluronan fragments. However common technological approaches of HA fragments production have their limitations. In many cases, the final products do not meet the strict pharmaceutical requirements, specifically due to size polydispersity and reaction contaminants. We present novel methodology based on combination of unique incidental ability of the plant-derived protease papain to split the glycosidic bonds and an indispensable advantages of biocompatible macroporous material with incorporated ferrous ions serving as carrier for covalent papain fixation. This atypical and yet unpublished highly efficient multiparametric approach allows enhanced HA fragmentation for easily and safely producing molar-mass-defined HA fragments with narrow size distribution. Native polyacrylamide gel electrophoresis (PAGE) and size exclusion chromatography/multi-angle light scattering (SEC-MALS) confirmed the effectiveness of our multiparametric approach.

Porphyromonas gingivalis: major periodontopathic pathogen overview.

Porphyromonas gingivalis is a Gram-negative oral anaerobe that is involved in the pathogenesis of periodontitis and is a member of more than 500 bacterial species that live in the oral cavity. This anaerobic bacterium is a natural member of the oral microbiome, yet it can become highly destructive (termed pathobiont) and proliferate to high cell numbers in periodontal lesions: this is attributed to its arsenal of specialized virulence factors. The purpose of this review is to provide an overview of one of the main periodontal pathogens-Porphyromonas gingivalis. This bacterium, along with Treponema denticola and Tannerella forsythia, constitute the "red complex," a prototype polybacterial pathogenic consortium in periodontitis. This review outlines Porphyromonas gingivalis structure, its metabolism, its ability to colonize the epithelial cells, and its influence upon the host immunity.