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The structure of two-dimensional polymer chains in a solvent at different temperatures is still far from being fully understood. Computer simulations of high-density macromolecular systems require the use of appropriate algorithms, and therefore the simulations were carried out using the Cooperative Motion Algorithm. The polymer model studied was exactly two-dimensional, coarse-grained and based on a triangular lattice. The theta temperature and temperature of coil-to-globule transition, and critical exponents were determined. The differences between the structure of such a disk and that of a chain in a dense polymer liquid were shown.
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We developed a simple model of the copolymerization process in the formation of crosslinked macromolecular systems. A living copolymerization was carried out for free chains, in bulk and in a slit, as well as for grafted chains in a slit. In addition, polymer 2D brushes were placed in a slit with initiator molecules attached to one of the confining walls. Coarse-grained chains were embedded in the vertices of a face-centered cubic lattice with the excluded volume interactions. The simulations of the copolymerization processes were performed using the Dynamic Lattice Liquid algorithm, a version of the Monte Carlo method. The influence of the initial initiator to cross-linker ratio, slit width and grafting on the polymerization and on the gelation was examined. It was also shown that the influence of a confining slit was rather small, while the grafting of chains affected the location of the gel pint significantly.
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Algoritmos , Polímeros , Simulação por Computador , Polimerização , Substâncias MacromolecularesRESUMO
The presented research focuses on the synthesis and structure-properties relationship of poly(carbonate-urea-urethane) (PCUU) systems including investigations on shape-memory effect capability. Furthermore, we approached the topic from a broader perspective by conducting extensive analysis of the relationship between the synthesized compounds and the results of computer simulations by means of the Monte Carlo method. For the first time, by using a unique simulation tool, the dynamic lattice liquid model (DLL), all steps of multi-step synthesis of these materials were covered by the simulations. Furthermore, broad thermal, mechanical, and thermomechanical characterization of synthesized PCUUs was performed, as well as determining the shape-memory properties. PCUUs exhibited good mechanical properties with a tensile strength above 20 MPa, elongation at break around 800%, and an exhibited shape-memory effect with shape fixity and shape recovery ratios above 94% and 99%, respectively. The dynamic lattice liquid model was employed to show the products and their molar mass distribution, as well as monomer conversion or the dispersity index for individual reaction steps. The results obtained in the following manuscript allow the planning of syntheses for the PCUUs of various structures, including crosslinked and soluble systems, which can provide a broad variety of applications of these materials, as well as a better understanding of the composition-properties relationship.
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Materiais Biocompatíveis , Poliuretanos , Materiais Biocompatíveis/química , Simulação por Computador , Teste de Materiais , Poliuretanos/química , Resistência à TraçãoRESUMO
Monodisperse polymer brushes were studied by means of Monte Carlo simulations. A coarse-grained model of a polymer brush was designed and the Cooperative Motion Algorithm was employed to model the polymerization process 'grafted from' and to study the structure of a brush immersed in a good solvent. The structure of brushes was determined as a function of the chain length and the grafting density. The influence of these parameters on the scaling properties of the brush was presented and discussed. A thorough analysis of the distribution of concentrations of the polymer segments and the distribution of chain free ends was also carried out. The analysis of the depth of penetration of the low molecular weight solvent into the brush area showed that the main factor determining the penetration is the grafting density. Good agreement between the simulation results and theoretical predictions is observed, especially for longer chains and higher grafting density. The origin of small quantitative differences between the simulation and theoretical results is discussed.
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We studied the movement of particles in crowded environments by means of extensive Monte Carlo simulations. The dynamic lattice liquid model was employed for this purpose. It is based on the cooperative movement concept and allows the study of systems at high densities. The cooperative model of molecular transport is assumed: the motion of all moving particles is highly correlated. The model is supposed to mimic lateral motion in a membrane and therefore the system is two-dimensional with moving objects and traps placed on a triangular lattice. In our study the interaction (binding) of traps with moving particles was assumed. The conditions in which subdiffusive motion appeared in the system were analysed. The influence of the strength of binding on the dynamic percolation threshold was also shown. The differences in the dynamics compared to systems with impenetrable obstacles and with systems without correlation in motion were presented and discussed. It was shown that in the case of correlated motion the influence of deep traps is similar to that of impenetrable obstacles. If the traps are shallow a recovery to normal diffusion was observed for longer time periods.
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Two-dimensional macromolecular systems were studied by means of Monte Carlo simulations employing the Cooperative Motion Algorithm. The influence of chain length and internal architecture on the location of the percolation thresholds was shown. A universal behavior of chain size at these thresholds was presented.
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The motion of small probe molecules in a two-dimensional system containing frozen polymer chains was studied by means of Monte Carlo simulations. The model macromolecules were coarse-grained and restricted to vertices of a triangular lattice. The cooperative motion algorithm was used to generate representative configurations of macromolecular systems of different polymer concentrations. The remaining unoccupied lattice sites of the system were filled with small molecules. The structure of the polymer film, especially near the percolation threshold, was determined. The dynamic lattice liquid algorithm was then employed for studies of the dynamics of small objects in the polymer matrix. The influence of chain length and polymer concentration on the mobility and the character of motion of small molecules were studied. Short- and long-time dynamic behaviors of solvent molecules were also described. Conditions of anomalous diffusions' appearance in such systems are discussed. The influence of the structure of the matrix of obstacles on the molecular transport was discussed.
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Several single nucleotide polymorphisms (SNPs) have been associated with an elevated risk of prostate cancer risk. It is not established if they are useful in predicting the presence of prostate cancer at biopsy or if they can be used to define a low-risk group of men. In this study, 4,548 men underwent a prostate biopsy because of an elevated prostate specific antigen (PSA; ≥4 ng/mL) or an abnormal digital rectal examination (DRE). All men were genotyped for 11 selected SNPs. The effect of each SNP, alone and in combination, on prostate cancer prevalence was studied. Of 4,548 men: 1,834 (40.3%) were found to have cancer. A positive association with prostate cancer was seen for 5 of 11 SNPs studied (rs1800629, rs1859962, rs1447295, rs4430796, rs11228565). The cancer detection rate rose with the number of SNP risk alleles from 29% for men with no variant to 63% for men who carried seven or more risk alleles (OR = 4.2; p = 0.002). The SNP data did not improve the predictive power of clinical factors (age, PSA and DRE) for detecting prostate cancer (AUC: 0.726 vs. 0.735; p = 0.4). We were unable to define a group of men with a sufficiently low prevalence of prostate cancer that a biopsy might have been avoided. In conclusion, our data do not support the routine use of SNP polymorphisms as an adjunct test to be used on the context of prostate biopsy for Polish men with an abnormal screening test.
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Polimorfismo de Nucleotídeo Único , Próstata/patologia , Neoplasias da Próstata/diagnóstico , Adulto , Idoso , Idoso de 80 Anos ou mais , Alelos , Área Sob a Curva , Biópsia , Exame Retal Digital , Humanos , Masculino , Pessoa de Meia-Idade , Antígeno Prostático Específico/sangue , Neoplasias da Próstata/genética , Neoplasias da Próstata/patologiaRESUMO
We performed extensive and systematic simulation studies of two-dimensional fluid motion in a complex crowded environment. In contrast to other studies we focused on cooperative phenomena that occurred if the motion of particles takes place in a dense crowded system, which can be considered as a crude model of a cellular membrane. Our main goal was to answer the following question: how do the fluid molecules move in an environment with a complex structure, taking into account the fact that motions of fluid molecules are highly correlated. The dynamic lattice liquid (DLL) model, which can work at the highest fluid density, was employed. Within the frame of the DLL model we considered cooperative motion of fluid particles in an environment that contained static obstacles. The dynamic properties of the system as a function of the concentration of obstacles were studied. The subdiffusive motion of particles was found in the crowded system. The influence of hydrodynamics on the motion was investigated via analysis of the displacement in closed cooperative loops. The simulation and the analysis emphasize the influence of the movement correlation between moving particles and obstacles.
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Simulação por Computador , Difusão , Hidrodinâmica , Modelos Químicos , Movimento (Física)RESUMO
Prostate cancer is the most common cancer diagnosed in men and the second leading cause of death in male cancer patients. The WHO suggests that cobalt is involved in the carcinogenesis of prostate cancer. There are, however, no studies associating cobalt levels and prostate cancer patient survival. In this study, 261 Polish prostate cancer (n = 261) patients were recruited into a prospective cohort between 2009 and 2015. Serum cobalt levels were measured using ICP-MS after prostate cancer diagnosis and before treatment. All study participants were assigned into quartiles (QI-QIV) based on the distribution of serum cobalt levels among censored patients. Univariable and multivariable COX regression models were used to calculate hazard ratios (HRs) for each serum cobalt level quartile. We found a significant relationship between high serum cobalt levels and poor prostate cancer patient total survival (HR = 2.60; 95% CI: 1.17-5.82; p = 0.02). In relation to prostate cancer patients who died as a result of other non-cancer causes, the association with high levels of cobalt was even stronger (HR = 3.67; 95% CI: 1.03-13.00; p = 0.04). The impact of high serum cobalt levels on overall survival of prostate cancer-specific-related deaths was not statistically significant.
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The most prevalent type of cancer among males is prostate cancer. Survival is considered quite good, but it can be further improved when risk factors are optimized. One of these factors is micronutrients, including Se and Zn. To our knowledge, the interaction between Se and Zn and prostate cancer remains undescribed. This study aimed to investigate the optimal levels of selenium (Se) and zinc (Zn) and their impact on the survival of individuals diagnosed with prostate cancer. A total of 338 prostate cancer patients were enrolled in this study, which was conducted in Poland between 2009 and 2015. Mass spectrometry, which uses inductively coupled plasma mass, was used to assess serum element levels before treatment. The study participants were categorized into quartiles (QI-QIV) based on the distributions of Se and Zn levels observed among surviving participants. Cox regression was used to assess the association between serum Se and Zn levels and the survival of prostate cancer patients. Our results reveal the effect of combined Se and Zn levels on survival in prostate cancer patients (SeQI-ZnQI vs. SeQIV-ZnQIV; HR = 20.9). These results need further research to establish Se/Zn norms for different populations.
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Neoplasias da Próstata , Selênio , Masculino , Humanos , Zinco , Micronutrientes/análise , Espectrometria de Massas/métodos , CobreRESUMO
BACKGROUND: The G84E mutation in the HOXB13 gene has been associated with a high lifetime risk of prostate cancer in North America (about 20-fold). The geographical and ethnic extent of this recurrent allele has not yet been determined. METHODS: We assayed for the presence of the G84E mutation in 3,515 prostate cancer patients and 2,604 controls from Poland and estimated the odds ratio for prostate cancer associated with the allele. RESULTS: The G84E mutation was detected in 3 of 2,604 (0.1%) individuals from the general population in Poland and in 20 of 3,515 (0.6%) men with prostate cancer (Odds ratio [OR] = 5.0; 95% CI: 1.5-16.7; P = 0.008). The allele was present in 4 of 416 (1.0%) men with familial prostate cancer (OR = 8.4, 95% CI: 1.9-37.7; P = 0.005). CONCLUSIONS: The G84E mutation predisposes to prostate cancer in Poland, but accounts for only a small proportion of cases. We expect that the G84E founder mutation might be present in other Slavic populations.
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Proteínas de Homeodomínio/genética , Mutação Puntual/genética , Neoplasias da Próstata/etnologia , Neoplasias da Próstata/genética , Adulto , Idoso , Idoso de 80 Anos ou mais , Predisposição Genética para Doença/etnologia , Predisposição Genética para Doença/genética , Genótipo , Humanos , Masculino , Pessoa de Meia-Idade , Razão de Chances , Linhagem , Polônia/epidemiologia , Fatores de Risco , População Branca/genética , População Branca/estatística & dados numéricosRESUMO
The structure of very thin polymer films formed by strongly adsorbed macromolecules was studied by computer simulation. A coarse-grained model of strictly two-dimensional polymer systems was built, and its properties determined by an efficient Monte Carlo simulation algorithm. Properties of the model system were determined by means of Monte Carlo simulations with a sampling algorithm that combines Verdier-Stockmayer, pivot and reputation moves. The effects of temperature, chain length and polymer concentration on the macromolecular structure were investigated. It was shown that at low temperatures, the chain size increases with the concentration, that is, inversely with high temperatures. This behavior should be explained by the influence of inter-chain interactions.
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A generic model was developed for studies of the polymerization process of regular branched macromolecules. Monte Carlo simulations were performed employing the Dynamic Lattice Liquid algorithm to study this process. A core-first methodology was used in a living polymerization of stars with up to 32 arms, and dendrimers consisted of 4-functional segments. The kinetics of the synthesis process for stars with different numbers of branches and dendrimers was compared. The size and structure of star-branched polymers and dendrimers during the synthesis were studied. The influence of the functionality of well-defined cores on the structure and on the dispersity of the system was also examined. The differences in the kinetics in the formation of both architectures, as well as changes to their structures, were described and discussed.
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Opposing polymer brush systems were synthesized and investigated by molecular modeling. Chains were restricted to a face-centered cubic lattice with the excluded volume interactions only. The system was confined between two parallel impenetrable walls, with the same number of chains grafted to each surface. The dynamic properties of such systems were studied by Monte Carlo simulations based on the dynamic lattice liquid model and using a highly efficient parallel machine ARUZ, which enabled the study of large systems and long timescales. The influence of the surface density and mean polymer length on the system dynamic was discussed. The self-diffusion coefficient of the solvent depended strongly on the degree of polymerization and on the polymer concentration. It was also shown that it is possible to capture changes in solvent mobility that can be attributed to the regions of different polymer densities.
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A model of the polymerization process during the formation of a pair of polymer brushes was designed and investigated. The obtained system consisted of two impenetrable parallel surfaces with the same number of chains grafted on both surfaces. Coarse-grained chains embedded in nodes of a face-centered cubic lattice with excluded volume interactions were obtained by a 'grafted from' procedure. The structure of synthesized macromolecular systems was also studied. Monte Carlo simulations using the dynamic lattice liquid model were employed using dedicated parallel machine ARUZ in a large size and time scale. The parameters of the polymerization process were found to be crucial for the proper structure of the brush. It was found that for high grafting densities, chains were increasingly compressed, and there is surprisingly little interpenetration of chains from opposite surfaces. It was predicted and confirmed that in a polydisperse sample, the longer chains have unique configurations consisting of a stretched stem and a coiled crown.
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The Sertoli cells were regarded as the only target for FSH in male reproductive system. The expression of FSH receptor (FSH-R) was detected also in epithelial cells of the caput epididymis of rat and monkey. We showed in the immunohistochemistry study the expression of FSH-R in rat and human ductuli efferentes and the caput, corpus, and cauda epididymis, moreover, by Western blot analysis in the caput and cauda epididymis of rat. Additionally, we presented that the morphology of rat epididymal epithelial cells in vitro was affected by FSH, and FSH stimulation resulted in the increase of 17beta-estradiol synthesis by rat caput epididymal cells in dose-depended manner. In conclusion, the identification of FSH receptors in human and rat epididymides supports our results that the epididymis is a target organ not only for LH but additionally for FSH. On the basis of the results we showed for the first time that morphology of epididymal epithelial cells and epididymal steroidogenesis can be regulated by FSH.
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Epididimo/metabolismo , Receptores do FSH/metabolismo , Epitélio Seminífero , Túbulos Seminíferos/metabolismo , Animais , Western Blotting , Células Cultivadas , Estradiol , Hormônio Foliculoestimulante/metabolismo , Humanos , Imuno-Histoquímica , Masculino , Músculo Esquelético/metabolismo , Ratos , Ratos Wistar , Epitélio Seminífero/citologia , Epitélio Seminífero/metabolismo , Estatísticas não ParamétricasRESUMO
The role of particular elements in lithogenesis is still unclear and debated. Probably some of them may promote or conversely inhibit crystal nucleation of organic or mineral species. A few epidemiological data link smoking with the risk of calcium stones. The aim of this hospital-based study was to evaluate the distribution of trace elements in urine and urinary stones, and possible correlation with stone constituents in smoking and non-smoking individuals. 209 stones and urine samples collected from idiopathic stone-formers were analyzed to evaluate the mineral composition and the distribution of elements, 29 in stones and 21 in urine. Values were statistically compared considering smoking, arterial hypertension and coronary heart disease as grouping variables. No differences were noted either for comparison of mineral components or the elements concentrations in stones in both groups. The concentration of mercury in urine was higher in smokers than in non-smokers, but the statistical significance was at the moderate level. Our findings do not support the concept of possible association between smoking and urinary lithogenesis, but we believe that further investigations are needed in this area.
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Fumar , Oligoelementos/metabolismo , Cálculos Urinários/metabolismo , Adulto , Estudos de Casos e Controles , Feminino , Humanos , Masculino , Mercúrio/metabolismo , Pessoa de Meia-Idade , Fatores de Risco , Fumar/efeitos adversos , Urolitíase/epidemiologia , Urolitíase/metabolismoRESUMO
In this study we investigated the percolation in the system containing long flexible polymer chains. The system also contained explicit solvent molecules. The polymer chains were represented by linear sequences of lattice points restricted to a two-dimensional triangular lattice. The Monte Carlo simulations were performed applying the cooperative motion algorithm. The percolation thresholds and the critical exponents of chains and solvent molecules were determined. The influence of the chain length on the percolation was discussed. It was shown that the percolation threshold decreased strongly with the chain length, which is closely connected to changes in chains' structure with the decreasing polymer concentration. The critical exponent beta for all chains under consideration and for solvent molecules was found almost constant and close to the theoretical value 5/36.
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Simulations of motion in a complex crowded environment were performed. We employed the dynamic lattice liquid model, which was based on the cooperative movement concept. This algorithm is capable of working at very high densities, and the motion of all objects was highly correlated. The so-called motion of a single agent, where the motion of molecules is considered as a random walk without any correlation with other moving objects, was also calculated as the state of reference. Immobilized chains embedded in a two-dimensional triangular lattice modeled the crowded environment. The dynamic behavior of movable objects was studied and the influence of the structure of the matrix of obstacles on the molecular transport was discussed. It was shown that the type of transport has an impact on the dynamics of the system. The appearance and properties of subdiffusive motion were analyzed and referred to the structure of polymer systems.