ABSTRACT
Supramolecular vessels emerged as tools to mimic and better understand compartmentalisation, a central aspect of living matter. However, many more applications that go beyond those initial goals have been documented in recent years, including new sensory systems, artificial transmembrane transporters, catalysis, and targeted drug or gene delivery. Peptides, carbohydrates, nucleobases, and steroids bear great potential as building blocks for the construction of supramolecular vessels, possessing complexity that is still difficult to attain with synthetic methods - they are rich in functional groups and well-defined stereogenic centers, ready for noncovalent interactions and further functions. One of the options to tame the functional and dynamic complexity of natural building blocks is to place them at spatially designed positions using synthetic scaffolds. In this review, we summarise the historical and recent advances in the construction of molecular-sized vessels by the strategy that couples synthetic predictability and durability of various scaffolds (cyclodextrins, porphyrins, crown ethers, calix[n]arenes, resorcin[n]arenes, pillar[n]arenes, cyclotriveratrylenes, coordination frameworks and multivalent high-symmetry molecules) with functionality originating from natural building blocks to obtain nanocontainers, cages, capsules, cavitands, carcerands or coordination cages by covalent chemistry, self-assembly, or dynamic covalent chemistry with the ultimate goal to apply them in sensing, transport, or catalysis.
ABSTRACT
Male infertility is a world multifactorial problem modulated by environmental and genetic factors. Male aspects account for 20-50â¯% of infertility cases. Our results are unique because they treat the importance of components participating in the determination of male infertility (environmental and immunogenetic determinants, seminological analysis, lipoperoxidation, genetic determinants, role of aluminum, arsenic, cadmium and boron). We analyzed agents affecting male reproductive potential (aluminum, boron, cadmium, arsenic, lipid peroxidation, gene polymorphisms (MTHFRv.C677T (rs1801133) (chromosome-1) and IL-4v.C589T (rs2243250) (chromosome-5) in men with semen disorders (n=76) and with normozoospermia (n=87) from Central Poland. Polymorphisms of MTHFRv.C677T and IL-4v.C589T genes indirectly shape toxic metals concentration and lipoperoxidation but do not exert direct influence on male fertility disorders (monomorphism and lack of differences in genotypes frequency). Men with genotype TT or CC (IL-4v.C589T) show some differentiation in elements concentration and intensity of lipoperoxidation. Analysis of TT or CC (IL-4v.C589T) genotype brought correlations with B, Al, Cd, and lipoperoxidation (P<0.05) and suggesting that mentioned factors jointly shape male reproductive capability. Toxic metals may play an important role in shaping of men genetic polymorphisms, since Cd was identified as a factor increasing risk of qualification to infertile group, predisposing to fertility disorders. B, Al and Cd may be considered as important modulators of reproductive condition. However, lipoperoxidation as an isolated predictive parameter does not produce convincing results in male reproductive potential (higher MDA concentration in healthy men). Our results may be helpful in the diagnosis of male infertility, in the reduction of idiopathic cases of unknown origin and in implementation of targeted and more effective treatment (pharmacological, hormonal). Identification of environmental stressors and their correlations with fertility disorders can help to eliminate or reduce the impact of factors unfavorable to fertility. Our results highlight the importance of environmental and immunogenetic factors in shaping of defensive potential against destruction of spermatozoa and infer a role of oxidative stress in the induction of gene polymorphisms, affecting male fertility.
ABSTRACT
Electronic circular dichroism (ECD) can be used to study various aspects of self-assembly (definition of stoichiometric ratios, chirality amplification during self-assembly, host-guest complexation). In this work, we show that ECD is a valuable tool for monitoring the self-assembly of chiral peptide-based capsules. By analyzing the signs, intensities, and temperature dependences of ECD bands, the effects of the non-specific processes can be separated from the restriction of intramolecular motion (RIM) caused by discrete self-assembly. Analysis of experimental and theoretical ECD spectra show that the differences between assembled and non-assembled species originate from induction of inherently chiral conformation and restriction of conformational freedom that leads to amplification of ECD signals during self-assembly of discrete species.
ABSTRACT
We explain environmental and genetic factors determining male genetic conditions and infertility and evaluate the significance of environmental stressors in shaping defensive responses, which is used in the diagnosis and treatment of male infertility. This is done through the impact of external and internal stressors and their instability on sperm parameters and their contribution to immunogenetic disorders and hazardous DNA mutations. As chemical compounds and physical factors play an important role in the induction of immunogenetic disorders and affect the activity of enzymatic and non-enzymatic responses, causing oxidative stress, and leading to apoptosis, they downgrade semen quality. These factors are closely connected with male reproductive potential since genetic polymorphisms and mutations in chromosomes 7, X, and Y critically impact on spermatogenesis. Microdeletions in the Azoospermic Factor AZF region directly cause defective sperm production. Among mutations in chromosome 7, impairments in the cystic fibrosis transmembrane conductance regulator CFTR gene are destructive for fertility in cystic fibrosis, when spermatic ducts undergo complete obstruction. This problem was not previously analyzed in such a form. Alongside karyotype abnormalities AZF microdeletions are the reason of spermatogenic failure. Amongst AZF genes, the deleted in azoospermia DAZ gene family is reported as most frequently deleted AZF. Screening of AZF microdeletions is useful in explaining idiopathic cases of male infertility as well as in genetic consulting prior to assisted reproduction. Based on the current state of research we answer the following questions: (1) How do environmental stressors lessen the quality of sperm and reduce male fertility; (2) which chemical elements induce oxidative stress and immunogenetic changes in the male reproductive system; (3) how do polymorphisms correlate with changes in reproductive potential and pro-antioxidative mechanisms as markers of pathophysiological disturbances of the male reproductive condition; (4) how do environmental stressors of immunogenetic disorders accompany male infertility and responses; and (5) what is the distribution and prevalence of environmental and genetic risk factors.
Subject(s)
Azoospermia , Environmental Exposure/adverse effects , Oxidative Stress , Spermatogenesis , Azoospermia/genetics , Azoospermia/immunology , Azoospermia/metabolism , Azoospermia/pathology , Chromosomes, Human/genetics , Chromosomes, Human/immunology , Chromosomes, Human/metabolism , Cystic Fibrosis Transmembrane Conductance Regulator/genetics , Cystic Fibrosis Transmembrane Conductance Regulator/metabolism , Humans , Male , Oxidative Stress/genetics , Oxidative Stress/immunology , Polymorphism, Genetic , RNA Recognition Motif Proteins/genetics , RNA Recognition Motif Proteins/immunology , RNA Recognition Motif Proteins/metabolism , Spermatogenesis/genetics , Spermatogenesis/immunologyABSTRACT
Examination of semen characteristics is routinely performed for fertility status investigation of the male partner of an infertile couple as well as for evaluation of the sperm donor candidate. A useful tool for preliminary assessment of semen characteristics might be an artificial neural network. Thus, the aim of the present study was to construct an artificial neural network, which could be used for predicting the result of semen analysis based on the basic questionnaire data. On the basis of eleven survey questions two models of artificial neural networks to predict semen parameters were developed. The first model aims to predict the overall performance and profile of semen. The second network was developed to predict the concentration of sperm. The network to evaluate sperm concentration proved to be the most efficient. 92.93% of the patients in the learning process were properly qualified for the group with a correct or incorrect result, while the result for the test set was 85.71%. This study suggests that an artificial neural network based on eleven survey questions might be a valuable tool for preliminary evaluation and prediction of the semen profile.
ABSTRACT
Molecular capsules composed of amino acid or peptide derivatives connected to resorcin[4]arene scaffolds through acylhydrazone linkers have been synthesized using dynamic covalent chemistry (DCC) and hydrogen-bond-based self-assembly. The dynamic character of the linkers and the preference of the peptides towards self-assembly into ß-barrel-type motifs lead to the spontaneous amplification of formation of homochiral capsules from mixtures of different substrates. The capsules have cavities of around 800â Å(3) and exhibit good kinetic stability. Although they retain their dynamic character, which allows processes such as chiral self-sorting and chiral self-assembly to operate with high fidelity, guest complexation is hindered in solution. However, the quantitative complexation of even very large guests, such as fullerene C60 or C70 , is possible through the utilization of reversible covalent bonds or the application of mechanochemical methods. The NMR spectra show the influence of the chiral environment on the symmetry of the fullerene molecules, which results in the differentiation of diastereotopic carbon atoms for C70 , and the X-ray structures provide unique information on the modes of peptide-fullerene interactions.
Subject(s)
Calixarenes/chemistry , Fullerenes/chemistry , Peptides/chemistry , Phenylalanine/analogs & derivatives , Kinetics , Magnetic Resonance Spectroscopy , Models, Molecular , Phenylalanine/chemistry , StereoisomerismABSTRACT
We analysed sodium (Na), copper (Cu) and selenium (Se) levels in human semen and glutathione peroxidase activity (GPx) in seminal plasma and examined their relationships with sperm quality. Semen samples were obtained from men (n=168) undergoing routine infertility evaluation. The study design included two groups based on standard ejaculate parameters: Group I (n=39) with normal ejaculates (normozoospermia) and Group II (n=129) with a pathological spermiogram. Se concentration (but not Na or Cu) and GPx activity were significantly higher in normozoospermic males than in those with a pathological spermiogram and also in males with correct sperm motility and normal sperm morphology than in asthenozoospermic and teratozoospermic males. There were significant correlations between sperm motility, Se and GPx, between rapid progressive motility and Cu, between sperm motility and Na, between normal sperm morphology and Se and Cu and between sperm concentration and Cu and GPx. Significant correlations were found between Na and Cu, between Na and Se and between Cu and Se in human semen in relation to alcohol consumption and tobacco use. Na, Cu, Se and GPx are related to sperm characteristics and male fertility and their survey could improve male infertility diagnosis.
ABSTRACT
The aim of the present study was to measure lanthanum (La), cerium (Ce), europium (Eu), and gadolinium (Gd) concentrations in human semen and correlate the results with sperm quality. The median semen content of La was 19.5 µg kg(-1) dry weight (dw) (range 2.27-269), of Ce was 41.9 µg kg(-1) dw (range 4.52 to 167), of Eu was 0.68 µg kg(-1) dw (range 0.06-1.95), of Gd was 3.19 µg kg(-1) dw (range 0.38-12.0), and of calcium (Ca) was 4063 mg kg(-1) dw (range 484-17,191). Concentrations of La, Ce, Eu, Gd, and Ca were significantly lower in nondrinkers' semen than in semen from drinkers. Significant differences were detected between La, Ce, Eu, Gd, and Ca concentrations in semen from nondrinkers and moderate drinkers. Concentrations of La, Ce, and Gd in semen of short-term smokers were significantly lower than those in extremely long-term smokers. Significant differences were also detected between La concentration in semen from a group of short-term smokers and that of a group of long-term smokers. Positive correlations were found between La, Ce, Eu, Gd, and Ca concentrations in semen. La, Ce, Gd, and Ca concentrations in semen were positively associated with progressive motility and percentage of normal spermatozoa. Positive correlations were found between Ca and sperm concentration. Concentrations of La, Ce, and Gd were negatively associated with sperm concentration, whilst Ca concentration was negatively associated with volume of ejaculate. At the examined level, La, Ce, Eu, and Gd did not affect sperm quality, whereas alcohol consumption and smoking might have increased the level of rare earth elements in semen.
Subject(s)
Environmental Exposure/analysis , Metals, Rare Earth/metabolism , Semen Analysis , Spermatozoa/metabolism , Humans , MaleABSTRACT
We show that the substitution of tetra(benzimidazole)resorcin[4]arenes with electron withdrawing groups on the upper rim enhances anion binding at the opposite edge by more than three orders of magnitude. Moreover, selective anion binding at either the OH/NH or CH binding sites is demonstrated.
ABSTRACT
The aim of the study was to analyze the activity of antioxidant enzymes (glutathione reductase, catalase, superoxide dismutase) and malondialdehyde (MDA) levels in a population of men with abnormal semen parameters and in a population of men diagnosed with normozoospermia. This study was performed using data collected at the Infertility Treatment Clinic 'Genesis' , Bydgoszcz, Poland, between 1 January 2011 and 31 December 2017. A total number of 321 men meeting the inclusion criteria were selected and divided into the control group (162 men) and the infertility group (159 men). The activities of superoxide dismutase (SOD), catalase (CAT), and glutathione reductase (GR) were measured using ready-made kits; lipid peroxidation intensity was determined by the thiobarbituric acid method. No statistically significant differences were found for the activity of SOD, GR, CAT between the groups. MDA values measured in the serum of patients in the healthy group were higher than in the group with semenological disorders. Although our study did not demonstrate the usefulness of the above blood tests, further studies are needed to explore the potential use of assessing redox parameters to develop new diagnostic and therapeutic approaches for male infertility.
ABSTRACT
BACKGROUND: Chronic insulin resistance, exacerbated in the course of pregnancy, is an important pathophysiologic mechanism of gestational diabetes mellitus (GDM). We hypothesise that the degree of insulin resistance, assessed at diagnosis of GDM, is a parameter of its pathophysiologic heterogeneity and/or severity. Thus, it offers potential to open new avenues for the personalization of therapy in affected women. METHODS: 1254 Polish Caucasian women with GDM were recruited into the study. The following parameters were assessed in the course of the study: body mass index (BMI), parity, weight gain during pregnancy, glycated haemoglobin, glucose level during an oral glucose tolerance test (OGTT), insulin, insulin resistance and insulin secretion. The severity of GDM was assessed based on insulin use and daily insulin dose during gestation. In order to evaluate insulin secretion and insulin resistance the homeostatic method was used (HOMA-B and HOMA-IR, respectively). We compared all the metabolic parameters and methods of treatment of GDM in women subdivided by quartiles of insulin resistance. RESULTS: The HOMA-IR in the whole population ranged from 0.34 to 20.39. The BMI, fasting insulin, fasting glucose and insulin dose per day increased along with increasing quartiles (HOMA-IR > 1.29). We observed a decrease of HOMA-B in the third quartile (1.92-2.89) compared with the first quartile (0.34-1.29). Insulin treatment was associated with HOMA-IR (<1.29 vs. >2.89), OR: 3.37, fasting glucose (≤6.11 vs. >6.11 mmol/dl), OR: 2.61, age (≤30 vs. >30 y. o.), OR: 1.54, and BMI (<25 vs. ≥25 kg/m2), OR: 1.45. Maximum insulin dose was associated with HOMA-IR, OR: 2.00, after adjustment for family history of diabetes, and 2-h OGTT glucose. CONCLUSION: Insulin resistance assessed by the HOMA index at diagnosis is associated with the severity and pathophysiological heterogeneity of GDM. A HOMA-IR >1.29 points to the major role of insulin resistance, indicating the need for a treatment aimed at improving tissue sensitivity to insulin. A HOMA-IR 1.29-2.89 suggests reduced insulin secretion, which is an indication for the introduction of insulin therapy. A HOMA-IR >2.89 indicates insufficient compensation for insulin resistance, which suggests the need for a treatment aimed at improving susceptibility of tissues to insulin combined with insulin therapy.
ABSTRACT
The relationships between CEUS parameters of adnexal tumours and postoperative immunohistochemical assessments of CD34, CD105 and bcl-2 were analysed. This study aimed to investigate whether contrast-enhanced ultrasonography (CEUS) parameters depend on the microvascular density of the tumour lesion found after surgery. Fifty-one patients with a diagnosis of adnexal tumours were included in this single-centre, prospective study. Participants underwent preoperative CEUS (contrast-enhanced ultrasound). Colour Doppler enhancement characterisation parameters (Ystart, Ymax and S) were determined. Immunohistochemical examination of histological specimens of the adnexal lesions was then carried out to determine the expression levels of the CD34, CD105 and bcl-2 proteins. Relationships between the aforementioned parameters were investigated. No significant statistical correlations were observed between CD34, CD105 and bcl2 expression levels and CEUS parameters, independently of whether the operated lesion was malignant or benign. Transvaginal CEUS is diagnostic for the detection of pathological neoplastic vascularisation of an adnexal lesion independent of the density of microcapillaries found postoperatively.
ABSTRACT
A coherence-based description of the Lyot depolarizer illuminated by polychromatic light of any spectral density distribution is proposed as a generalization of the formulas provided for symmetrical spectra by Burns [J. Lightwave Technol. 1, 475 (1983)] and Mochizuki [Appl. Opt. 23, 3284 (1984)]. The structure of the derived expressions is explained in physical terms, and a numerical comparison with the previous solutions is performed. The results of the numerical analysis show that the proposed description, when applied to any configuration of a two-segment anisotropic depolarizer, is fully equivalent with the Mueller-Stokes calculus for broadband light. Following this consistency, the range of accuracy of the formula by Mochizuki has been verified.
ABSTRACT
The inability to become pregnant for at least 1 year despite regular unprotected intercourse may indicate infertility of one or both partners. This problem affects approximately 10-20% of couples worldwide, regardless of race, with male infertility reported to account for 25-60% of cases. Among the most common pathological causes of male infertility is the presence of varicocele and chronic infections of the male reproductive system. This study was performed using data collected at the Genesis Infertility Treatment Clinic, Bydgoszcz, Poland, between 1 January 2015 and 30 June 2017. A total of 163 men meeting the inclusion criteria were selected and divided into the idiopathic infertility group (78 men) and varicocele-related infertility group (85 men). All patients received treatment with a male fertility supplement containing a combination of 1725 mg of L-carnitine fumarate, 500 mg of acetyl-L-carnitine, 90 mg of vitamin C, 20 mg of coenzyme Q10, 10 mg of zinc, 200 µg of folic acid, 50 µg of selenium, and 1.5 µg of vitamin B12 (Proxeed® Plus, Sigma-Tau, Italy) twice a day for a period of 6 months from the time of the diagnosis of infertility. The treatment resulted in significant improvements in general semen parameters, particularly sperm count, sperm concentration, total motility, and progressive motility. This antioxidant therapy produced a particularly marked therapeutic benefit in patients with Grade III varicocele, with a greater improvement in progressive motility than in men with less severe or no varicocele. The use of the antioxidant preparation examined here seems reasonable in men with idiopathic infertility and as an adjuvant in those with varicocele-related infertility in whom surgical treatment has resulted in no improvement. Its use should be considered particularly in patients with Grade III varicocele who do not wish to undergo surgical treatment or in whom such a treatment is not possible for various reasons.
ABSTRACT
The intensification of oxidative stress and destabilization of the antioxidative defenses of an organism is a consequence of many environmental factors. We considered aspects conditioning male reproductive potential and the functionality of enzymatic antioxidative mechanisms, i.e., superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) and glutathione reductase (GR), and their correlations with Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Ag, Cd, Sn, Sb, Ba, Hg, Tl, Pb, and malondialdehyde (MDA), as well as genetic polymorphism IL-4v.C589T (rs2243250) in men with infertility (n = 76). A healthy normozoospermic control (n = 87) was also used. We assessed the impact of negative changes driven by oxidative stress on enzymatic antioxidative mechanisms as well as the role of MDA in the overall process. On this basis, we infer connections between disturbances in enzymatic antioxidative defense and reproductive potential. Based on a molecular analysis of the polymorphism of gene IL-4v.C589T (rs2243250) (chromosome 5) (PCR-RFLP), we considered the relationships among particular genotypes with the possibility of occurrence of male infertility. Concentrations of chemical elements were measured in the blood. The activity of antioxidants and MDA levels were measured in serum. In the infertile group, higher GPx activity was noted (6.56 nmoL·min-1·mL-1, control: 4.31 nmoL·min-1·mL-1; p = 0.004), while GR achieved a greater level in the control (17.74 nmoL·min-1·mL-1, infertile: 15.97 nmoL·min-1·mL-1, p = 0.043), which implies diversified efficiency of the first and second lines of defense. The polymorphism of IL-4v.C589T (rs2243250) was not directly connected with infertility because there were not any differences in the frequency of genotypes between the infertile and control group (p = 0.578). An analysis of genotypes CC and TT (polymorphism IL-4v.C589T (rs2243250)) indicated numerous correlations between antioxidants, chemical elements and MDA. Therefore, chemical economy, antioxidative defense and genetic conditions are connected and jointly shape male reproductive potential. Chemical elements influence antioxidative defense and male fertility; the most important modulators appeared to be Na, Ba, Al and B. The polymorphism of gene IL-4v.C589T (rs2243250) has a limited influence on antioxidative defense and the metabolism of chemical elements.
ABSTRACT
The male factor is responsible for infertility in about 35-40% of all cases. Idiopathic oligo- and/or astheno- and/or therato-zoospermia is one of the most common male fertility disorders and remains a significant therapeutic challenge. The primary cause of idiopathic male infertility remains unknown but seems to be associated with oxidative stress. Objective: The use of antioxidative formulation to improve qualitative and quantitative deficiencies in the male gametes.In total, 78 subjects were treated with a combination of 1,725 mg L-carnitine fumarate, 500 mg acetyl-L-carnitine, 90 mg vitamin C, 20 mg coenzyme Q10, 10 mg zinc, 200 µg folic acid, 50 µg selenium, and 1.5 µg vitamin B12 (Proxeed® Plus, Sigma-Tau, Italy) for 6 months; the preparation was taken twice daily from the time idiopathic infertility was diagnosed. Basic seminal parameters were evaluated by a European Society of Human Reproduction and Embryology (ESHRE) -certified embryologist following the fifth edition of the World Health Organisation (2010) guidelines at three time points: at baseline and 3 and 6 months of treatment.Improvements in semen parameters (differing in terms of dynamics) were evident at 3 months and gradually improved over the 6 months of treatment. Each parameter: sperm concentration, total sperm count, sperm total and progressive motility improved significantly after treatment except for the percentage of sperm of abnormal morphology and ejaculate volume.Proxeed Plus was effective for patients with idiopathic infertility; however, a long treatment period is needed to achieve optimal results.
Subject(s)
Acetylcarnitine , Infertility, Male , Antioxidants , Carnitine , Fumarates , Humans , Infertility, Male/drug therapy , Male , Sperm MotilityABSTRACT
UNLABELLED: 1. Evaluation of frequency of cesarean sections for ocular indications. 2. Analysis of ophthalmological disorders as indications for cesarean section. MATERIAL AND METHODS: 4895 cesarean sections were performed (100 due to ocular indications) in the Department of Obstetrics, Female Pathology and Oncological Gynecology between 2000 and 2008. Medical documentation was analyzed. RESULTS: Among 4895 patients undergoing cesarean sections, 100 (2.04%) presented a written certification from an ophthalmologist suggesting this way of delivery. The frequency of c-sections due to ocular indications continued to increase between 2000-2005 and has been in decline since 2006. The most common ophthalmological disorders included myopia (57%), retinopathy (20%), glaucoma (5%), imminent retinal detachment (4%) and past retinal detachment (3%). In 45% of patients an eye pathology was the only reason for a cesarean section. CONCLUSION: 1. The frequency of cesarean sections due to ocular reasons in our material was 0.7%- 3.44%, average 2.04%. 2. Since 2006 the number of ocular indications for cesarean section has been decreasing. Nevertheless, it remains to be twice as high as in 2000. 3. The most common eye disorders leading to cesarean section were myopia and retinopathy 4. In almost half of the patients the decision to conduct a cesarean section was based solely on ophthalmological indications.
Subject(s)
Cesarean Section/statistics & numerical data , Eye Diseases/epidemiology , Pregnancy Complications/epidemiology , Referral and Consultation/statistics & numerical data , Academic Medical Centers , Female , Humans , Maternal Welfare , Poland , Pregnancy , Retrospective Studies , Risk FactorsABSTRACT
Among solution-processable techniques, inkjet printing is a potential method for manufacturing low-cost and high-resolution polymer organic light-emitting diodes (PLEDs) for displays/solid-state lighting applications. Herein, we demonstrate use of the inkjet printed cesium carbonate (Cs2CO3) film as an electron injection interlayer. We have elaborated the Cs2CO3 ink using an alcohol-based solvent for the industrial-grade printhead. The printed Cs2CO3 layer morphology was investigated by means of an optical microscope and an atomic force microscope. The PLEDs based on emissive polymer (Super Yellow) with printed Cs2CO3 interlayer show a remarkable current efficiency and luminance compared to the PLEDs made without the Cs2CO3 layer. Such results suggest that the Cs2CO3 is a promising material for the formulation of the electron injecting inkjet inks. The possibility of inkjet printing of an efficient electron injecting layer enables in situ patterning of PLEDs' emission area. Such a simple and flexible technique can be applied for a wide range of applications such as signage, pictograms, advertising, smart packaging, etc.
ABSTRACT
A supramolecular complex, formed by encapsulation of C60 fullerene in a molecular container built from two resorcin[4]arene rims zipped together by peptidic arms hydrogen bonded into a cylindrical ß-sheet, was studied by X-ray crystallography, solid-state and solution NMR, EPR spectroscopy and differential scanning calorimetry (DSC). The crystal structure, determined at 100â K, reveals that the complex occupies 422 site symmetry, which is compatible with the molecular symmetry of the container but not of the fullerene molecule, which has only 222 symmetry. The additional crystallographic symmetry leads to a complicated but discrete disorder, which could be resolved and modelled using advanced features of the existing refinement software. Solid-state NMR measurements at 184-333â K indicate that the thermal motion of C60 in this temperature range is fast but has different activation energies at different temperatures, which was attributed to a phase transition, which was confirmed by DSC. Intriguingly, the activation energy for reorientations of C60 in the solid state is very similar for the free and encaged molecules. Also, the rotational diffusion coefficients seem to be very similar or even slightly higher for the encaged fullerene compared to the free molecule. We also found that chemical shift anisotropy (CSA) is not the main relaxation mechanism for the 13C spins of C60 in the studied complex.
ABSTRACT
INTRODUCTION: Gestational diabetes mellitus (GDM) is a heterogeneous disease. We hypothesized that fasting hyperglycaemia, defined as impaired fasting glycaemia (IFG), is a marker of metabolic heterogeneity of GDM. The aim of this study was to compare selected metabolic parameters in two groups of women with GDM, one with normal fasting glycaemia (NFG GDM) and another with IFG, to test this hypothesis. MATERIAL AND METHODS: Metabolic parameters of 1025 women with GDM (mean age 29 years): glucose and insulin at 0 OGTT, glucose at 2-h oral glucose tolerance test (OGTT), body mass index before pregnancy, parity, and gestational age at diagnosis of GDM were analyzed. Insulin resistance and beta-cell function were evaluated by HOMA indexes (HOMA-IR and HOMA-B) at the diagnosis of GDM. RESULTS: The IFG GDM group (23%) consisted of isolated IFG (30%), IFG/IGT (60%), and IFG/DM (10%). The NFG GDM group (77%) consisted of isolated IGT (98%) and NFG/DM (2%). Women with IFG GDM were characterized by higher prepregnancy BMI, earlier diagnosis of GDM, higher HOMA-IR (p < 0.03), and lower HOMA-B (p < 0.01) compared to NFG GDM. In the IFGGDM group, DM was characterized by lower HOMA-B compared with isolated IFG and IFG/IGT. In the NFG GDM group, isolated IGT and DM were characterized by similar HOMA-IR and HOMA-B. CONCLUSIONS: Impaired fasting glucose distinguishes more severe metabolic phenotypes of GDM compared toGDM with normal fasting glucose concentrations.