Effect of the manufacturing process on Fiore Sardo PDO cheese microstructure by multi-frequency NMR relaxometry.

The quality of Fiore Sardo cheese, a traditional Italian dairy product, was analyzed by means of Multi-frequency Nuclear Magnetic (NMR) relaxometry. Specifically, ten cheese wheels were purchased from different production chains, either industrial (N = 5) or artisanal (N = 5) samples. The former came from large scale productions and the latter were produced by shepherds in small quantities and in very small dairy factories. A preliminary interlaboratory proficiency testing of Time Domain - NMR (TD-NMR, 20 MHz) relaxometry by five laboratories, consistently showed that product quality is significantly different in terms of molecular mobility according to their production chain (i.e. industrial or artisanal). More detailed information about cheese microstructure was obtained by Multi-frequency Fast Field Cycling NMR (FFC-NMR) at lower magnetic fields (0.01-10 MHz). According to the interpretative model adopted to describe FFC-NMR data, industrially processed cheeses showed a higher para-casein hydration, higher protein protons to water protons ratio and a higher disorder (lower fractal dimension df) than artisanal products. It is suggested that differences between artisanal and industrial cheeses generate from the processing steps preceding cheese maturation, and are clearly reflected in the visual appearance of cheeses. This study shows that NMR relaxometry techniques can successfully discriminate Fiore Sardo cheese from different production chains, and paves the way for their implementation in quality control practices of dairy products.

[German pain questionnaire and standardised documentation with the KEDOQ-Schmerz. A way for quality management in pain therapy]. / Deutscher Schmerzfragebogen (DSF) und standardisierte Dokumentation mit KEDOQ-Schmerz. Auf dem Weg zur gemeinsamen Qualitätsentwicklung der Schmerztherapie.

KEDOQ-Schmerz was developed by the German Pain Society (formerly DGSS) as a basic tool for documentation and quality management of pain therapy. It is planned to use KEDOQ-Schmerz as the data basis for nationwide, cross-sectional and independent scientific research in health services in Germany. With comparatively little effort, each participating institution (practices, pain clinics) will be able to provide quality control of their own diagnostic procedures and therapeutic effects by using benchmarking. In future KEDOQ-Schmerz will also be used as a method for external quality management in pain therapy in Germany.

[Interdisciplinary treatment. Long-lasting, effective, and cost-effective]. / Multimodale Therapie : Nachhaltig wirksam und kosteneffektiv.

The efficacy of intensive interdisciplinary pain management programs for patients with chronic low back pain has been repeatedly demonstrated. A controversial issue in previous studies is the cost-effectiveness of this treatment. Between 2001 and 2006, a total of 575 patients with chronic nonspecific back pain took part in an outpatient pain management program at the German Red Cross Pain Center (DRK Schmerz-Zentrum Mainz) in Mainz, Germany. Complete follow-up data were available for 351 patients 1 year after the end of treatment and were included in the study. No differences between these patients and the dropouts were found. Pain, impairment, and mental well-being had significantly improved after 1 year. For employed patients, the number of absent days decreased to almost one-quarter. On the basis of the study by Wenig, who calculated pain-related costs as a function of Von Korff pain grades, the treatment resulted in a savings of euro 3,329.50 per year per patient. Intensive multidisciplinary treatment of chronic back pain is highly effective and, at least for patients with high levels of disability, is also cost-effective.

Dynamical surface affinity of diphasic liquids as a probe of wettability of multimodal porous media.

We introduce a method for estimating the wettability of rock/oil/brine systems using noninvasive in situ nuclear magnetic relaxation dispersion. This technique scans over a large range of applied magnetic fields and yields unique information about the extent to which a fluid is dynamically correlated with a solid rock surface. Unlike conventional transverse relaxation studies, this approach is a direct probe of the dynamical surface affinity of fluids. To quantify these features we introduce a microscopic dynamical surface affinity index which measures the dynamical correlation (i.e., the microscopic wettability) between the diffusive fluid and the fixed paramagnetic relaxation sources at the pore surfaces. We apply this method to carbonate reservoir rocks which are known to hold about two thirds of the world's oil reserves. Although this nondestructive method concerns here an application to rocks, it could be generalized as an in situ liquid/surface affinity indicator for any multimodal porous medium including porous biological media.

Observation of exchange of micropore water in cement pastes by two-dimensional T(2)-T(2) nuclear magnetic resonance relaxometry.

The first detailed analysis of the two-dimensional (2D) NMR T(2)-T(2) exchange experiment with a period of magnetization storage between the two T(2) relaxation encoding periods (T(2)-store-T(2)) is presented. It is shown that this experiment has certain advantages over the T(1)-T(2) variant for the quantization of chemical exchange. New T(2)-store-T(2) 2D 1H NMR spectra of the pore water within white cement paste are presented. Based on these spectra, the exchange rate of water between the two smallest porosity reservoirs is estimated for the first time. It is found to be of the order of 5 ms{-1}. Further, a careful estimate of the pore sizes of these reservoirs is made. They are found to be of the order of 1.4 nm and 10-30 nm , respectively. A discussion of the results is developed in terms of possible calcium silicate hydrate products. A water diffusion coefficient inferred from the exchange rate and the cement particle size is found to compare favorably with the results of molecular-dynamics simulations to be found in the literature.

Microstructure evolution of hydrated cement pastes.

We propose an original method based on both proton nuclear magnetic relaxation dispersion and high-resolution NMR spectra to investigate the microstructure of synthesized Ca3SiO5-hydrated cement paste. This method allows a clear assessment of the local proton chemical sites as well as the determination of dynamical information of moving proton species in pores. We show also how the microstructure evolves during and after completion of hydration in a range of length scales between 2 and 500 nm. In particular, we show how the pore size distribution of the cement paste reaches progressively a power-law characteristic of a surface-fractal distribution with a dimension Df = 2.6, which takes into account the hierarchical order in the material. Last, we study how this pore size distribution is modified during setting by varying either the water-to-cement ratio or addition of ultrafine particles. This shows that our method could be relevant to relate the mechanical properties to the microstructure of the material. This proposed NMR method is general enough for the characterization of microstructure of any porous media with reactive surface involving water confinement.

Surface relaxation and chemical exchange in hydrating cement pastes: a two-dimensional NMR relaxation study.

We report the first nuclear magnetic resonance (NMR) two-dimensional correlation T(1) - T(2) and T(2) - T(2) measurements of hydrating cement pastes. A small but distinct cross peak in the two-dimensional relaxation spectrum provides the first direct evidence of chemical exchange of water between gel and capillary pores occurring over the first 14 days of hydration. A correlation of features along the line T(1) = 4T(2) provides strong supportive evidence for the surface diffusion model of (1)H nuclear spin relaxation in cements and for a multimodal discrete pore size distribution. Differences in detail of the results are reported for white cement paste and white cement paste with added silica fume. Both the method and the theory presented can be applied more widely to other high surface area materials with other reactive surface areas.

Evolution of eusociality and the soldier caste in termites: a validation of the intrinsic benefit hypothesis.

In termites the evolution of reproductive altruism is not based on a particularly high relatedness between nestmates. For the evolution and maintenance of the ancestral sterile soldier caste, the benefits generated by the soldiers' presence must compensate the loss of the soldiers' reproductive potential. To study the impact of soldiers on colony's fitness, we manipulated the proportion of soldiers to nonsoldiers in colonies of the dry-wood termite Cryptotermes secundus.'Soldier-less' colonies were obtained by removing soldiers and inhibiting their development with an extract of soldier heads. The colonies were set up for 1 year in experimental nests in the field. 'Soldier-less' colonies produced fewer soldiers. The reduction of soldiers neither affected colony survival nor helper growth, but fewer dispersing sexuals were produced in 'soldier-less' than in control colonies. This confirms what was only supposed so far, that in termites soldiers are maintained for their intrinsic benefit to cost ratio.

Universal nuclear spin relaxation and long-range order in nematics strongly confined in mass fractal silica gels.

We show how the low-frequency dependence of the proton spin-lattice relaxation time T1(nu) of octylcyanobiphenyl liquid crystals confined in high-density silica gels evidences a long-range order nematic phase in spite of the strong confinement and random disorder of the gels. The universal value and frequency dependence observed, T1(nu) proportional, variant nu(2/3), is interpreted within a relaxation model due to director fluctuations in nematic liquid crystals confined to mass fractal porous media. The model provides a relation T1(nu) proportional, variant nu(2-d/2), giving a reliable value of the structural fractal dimension d(f)=2.67 for all the host silica gels.

Surface nuclear magnetic relaxation and dynamics of water and oil in granular packings and rocks.

Low field proton nuclear spin-relaxation at variable magnetic field strength and temperature provides surface dynamical parameters such as surface diffusion coefficients, activation energies, time of residence and coefficient of surface affinity. These parameters were extracted from measurements on grain packs and natural oil-bearing rocks. On grain packs, we show first that changing the amount of surface paramagnetic impurities leads to striking different relationships between the pore-size and the relaxation times T1 and T2. These relationships are well supported by fast-diffusion (surface-limited) or slow-diffusion relaxation models. Surface relaxivity parameters rho1 and rho2 are deduced from the pore size dependence in the fast-diffusion regime. Then, we evidence the frequency and temperature dependence of the surface relaxivity rho1 by field cycling NMR relaxation and relevant theoretical models. The typical frequency dependence found allows an experimental separation of the surface and bulk microdynamics in granular packings and petroleum rocks and the determination of the above mentioned surface dynamical parameters. Finally, we present the first field cycling nuclear spin relaxation experiments performed in water/oil saturated petroleum rocks. We believe that these experiments give new information about the surface localization of these two saturating liquids in pores.

What is the surface specific area of porous cement-based material? A nuclear magnetic relaxation dispersion approach.

We propose a new NMR method to measure and follow the evolution of the surface specific area, Sp, of a porous cement-based material. This method, that does not require any preliminary drying process, uses nuclear magnetic relaxation dispersion (NMRD), the measurement of spin-lattice relaxation rate as a function of magnetic field strength or nuclear Larmor frequency. The method is applied for three different mortars samples prepared by mixing cement, sand, silica fume, water and superplasticizer with a water to cement ratio w/c=0.25, 0.38 and 0.65, respectively. The evolution of Sp grows linearly with the degree of advancement of chemical reactions measured by thermal heating and we evidence two relaxation processes independent of the w/c ratio.

Micropore size analysis by NMR in hydrated cement.

The understanding of the microstructure of cement remains incomplete. Especially, the progressive setting of the material is still unclear. Micropore size distribution (microstructure) has been investigated by both standard proton nuclear magnetic relaxation (1H-NMR) and field-cycling relaxation in C3S hydrated paste. The non-exponential decay was interpreted as a distribution of discrete relaxation rates. The attribution of T1 is supported by both a spectral and a dispersion curve analyses. These experiments allow us to follow the structuration of the material during setting.

Probing the surface area of a cement-based material by nuclear magnetic relaxation dispersion.

We show how nuclear magnetic spin-lattice relaxation dispersion of 1H water can provide a direct reliable value of the specific surface area of a cement-based material. The remarkable features of the relaxation dispersion support an interpretation in terms of coupled solid-liquid relaxation at pore interfaces, surface diffusion, and nuclear paramagnetic relaxation. The measurement is sufficiently fast to be applied continuously during the progressive hydration and setting of the material. This method is relevant to other chemically reactive porous media in chemical engineering and oil recovery.

Slow dynamics of embedded fluid in mesoscopic confining systems as probed by NMR relaxometry.

Mesoscopic media such as porous materials or colloidal dispersions strongly influence the dynamics of the embedded fluid. In the strong-adsorption regime, it was recently proposed that the effective surface diffusion on flat surface is anomalous and exhibits long-time pathology, enlarging the time domain of the embedded-fluid dynamics towards the low-frequency regime. An interesting way to probe such a slow interfacial process is to use the field-cycling NMR relaxometry. This technique is used here to probe the fluid dynamics in two types of interfacial systems: i) a colloidal glass made of thin and flat particles; ii) a fully saturated porous media, the Vycor glass. Experimental results are critically compared to either a simple theoretical model of NMR dispersion involving elementary steps of the fluid dynamics near an interface (loops, trains, tails) or Brownian-dynamics simulations performed inside 3D reconstructions of these confined systems.

[Health-related quality of life in patients with chronic pain]. / Gesundheitsbezogene Lebensqualität bei Patienten mit chronischen Schmerzen.

AIMS: An empirical comparison of the performance characteristics of 3 generic health-related quality of life (HRQL) measures in pain patients. METHODS: The Nottingham Health Profile (NHP), the Medical Outcomes Study 36-item Short-Form Health Survey (SF-36), and the German Life Satisfaction Scale (FLZ-M) by Henrich et al. were simultaneously employed in a multicenter survey measuring the impact of pain on quality of life. The HRQL- instruments were incorporated into the German Pain Questionnaire (pain variables, CES-D, Pain Disability Index). RESULTS: Characteristics of 3294 pain patients of 13 pain facilities are detailed in tables 1-3. Six of the 8 SF-36- and 4 of the 6 NHP-scales show satisfactory item-total correlations, bottom- and ceiling-effects, and internal consistency. FLZ-M reliabilities are satisfactory. The item weighting procedure of the FLZ-M proves to be unnecessary. Principle component analyses result in 7 factors for the SF-36 and the NHP. Six of the SF-36-factors are fairly homogeneous. The heterogeneity of the NHP- factors is marked. Correlations of the HRQL scales with depression (CES-D), anxiety (STAI) and physical functioning (FFbH-R-18) are high in all related contents. All instruments discriminate well between headache and back pain patients, between several pain grades (v. Korff) and the 3 Mainz pain chronicity stages. CONCLUSIONS: The SF-36 has satisfactory to good psychometric properties in pain patients, the NHP item selection has to be improved. The FLZ-M weighting can be eliminated. The shortcomings of the SF-36 can be overcome by adding short scales on role functioning and pain (modular approach).

Tumour-inhibitory effects of dendritic cells administered at the site of HPV 16-induced neoplasms.

Experiments were designed to examine whether administration of APC at the site of HPV 16-associated tumours can inhibit tumour growth and whether the efficacy of established dendritic cell lines is comparable to that of fresh BMDC populations. Mice were inoculated s.c. with APC, either bone marrow-derived dendritic cells differentiated in medium supplemented with GM-CSF and IL-4 (BMDC), or with established dendritic cell lines DC2.4 or JAWS II. The pretreated mice, together with untreated controls, were challenged with syngeneic HPV 16-transformed cells MK16 at the site of APC administration. It has been found that both BMDC and dendritic cell lines can inhibit tumour growth and that the efficacy of the established dendritic cell lines DC2.4 and JAWS II was comparable to that of fresh BMDC populations. In vitro induction of proliferative spleen cell responses by co-cultivation with MK16 antigen-pulsed BMDC or MK16 antigen-pulsed dendritic cell lines revealed that both types of APC populations can prime immune reactions directed against syngeneic HPV 16-associated neoplasms. Taken together, the results suggest that local increase in the number of dendritic cells at the site of HPV 16-associated tumours can inhibit progression of the tumours and that the dendritic cell lines which are efficient in this respect can be considered and should be tested in both, preclinical and human systems for delivery of therapeutic vaccines against HPV 16-associated neoplasms.

Ori-somes, nucleoprotein complexes descending from origin regions of animal chromosomal DNA replication. A micromorphological study.

Micromorphology of nucleoprotein (NP) complexes designated according to their descent and shape as Ori-somes is presented. These NP complexes of three different types harbor molecules of cytoplasmic "small" polydisperse DNA, which descend from origin regions of chromosomal DNA replication and are equipped, as shown previously, with early DNA-synthesizing activities. By negative staining the Ori-somes are visualized as particles of irregular shape, sometimes of a subunit-like structure. Micromorphological differences in size and structural compactness noted among individual Ori-somes are dependent on their type similarly as earlier shown physico-chemically and biochemically. Such differences were also confirmed by two different spreading techniques. The most unravelled structures with electron diffuse centers belong to Ori-somes of component B associated with most active DNA synthesis. In contrast, the Ori-somes of components A and C, associated with pronounced RNA synthesis, revealed large electron-dense centers. The incidence of replicative structures present in Ori-somes corresponds with the level of their DNA-synthesizing activities.

Erythema migrans after ceftriaxone treatment of aseptic meningitis caused by Borrelia burgdorferi.

Erythema migrans is the characteristic exanthem of Lyme disease. The rash initially occurs at the site of inoculation; subsequently satellite lesions can occur. We describe an adolescent girl in whom the rash appeared after the initiation of ceftriaxone therapy for aseptic meningitis. We suggest that the occurrence of rash in this patient was a result of liberated toxin from local bacterial lysis.

Caveolae are involved in the trafficking of mouse polyomavirus virions and artificial VP1 pseudocapsids toward cell nuclei.

Electron and confocal microscopy were used to observe the entry and the movement of polyomavirus virions and artificial virus-like particles (VP1 pseudocapsids) in mouse fibroblasts and epithelial cells. No visible differences in adsorption and internalization of virions and VP1 pseudocapsids ("empty" or containing DNA) were observed. Viral particles entered cells internalized in smooth monopinocytic vesicles, often in the proximity of larger, caveola-like invaginations. Both "empty" vesicles derived from caveolae and vesicles containing viral particles were stained with the anti-caveolin-1 antibody, and the two types of vesicles often fused in the cytoplasm. Colocalization of VP1 with caveolin-1 was observed during viral particle movement from the plasma membrane throughout the cytoplasm to the perinuclear area. Empty vesicles and vesicles with viral particles moved predominantly along microfilaments. Particle movement was accompanied by transient disorganization of actin stress fibers. Microfilaments decorated by the VP1 immunofluorescent signal could be seen as concentric curves, apparently along membrane structures that probably represent endoplasmic reticulum. Colocalization of VP1 with tubulin was mostly observed in areas close to the cell nuclei and on mitotic tubulin structures. By 3 h postinfection, a strong signal of the VP1 (but no viral particles) had accumulated in the proximity of nuclei, around the outer nuclear membrane. However, the vast majority of VP1 pseudocapsids did not enter the nuclei.

Surface nuclear magnetic relaxation and dynamics of water and oil in macroporous media.

Proton nuclear spin-relaxation studies on water- or oil-saturated granular packings and limestone rocks allow estimating surface molecular dynamical parameters. Measurements were performed at various conditions of temperature, magnetic field strengths, and pore size. We show by low field NMR relaxation that changing the amount of surface paramagnetic impurities leads to striking different pore-size dependences of the relaxation times T1 and T2 of liquids in pores. These dependences are well supported by surface-limited or diffusion-limited relaxation models. Surface relaxivity parameters rho(1) and rho(2) are deduced from the pore-size dependence in the surface-limited regime. We evidence the frequency and temperature dependence of the surface relaxivity rho(1) by field cycling NMR relaxation and relevant theoretical models. The typical frequency dependence found allows an experimental separation of the surface and bulk microdynamics in porous media. Several surface dynamical parameters, such as diffusion coefficients, activation energies, time of residence, and coefficient of surface affinity, were therefore determined. The methods presented here give a powerful analysis of the surface microdynamics of confined liquids, which can be applied to the study of oil-bearing rocks.