Non-invasive Investigations of Paintings by Portable Instrumentation: The MOLAB Experience.

The in situ non invasive methods have experienced a significant development in the last decade because they meet specific needs of analytical chemistry in the field of cultural heritage where  artworks are rarely moved from their locations, sampling is rarely permitted, and analytes are a wide range of inorganic, organic and organometallic substances in complex and precious matrices. MOLAB, a unique collection of integrated mobile instruments, has greatly contributed to demonstrate that it is now possible to obtain satisfactory results in the study of a variety of heritage objects without sampling or moving them to a laboratory. The current chapter describes an account of these results with particular attention to ancient, modern, and contemporary paintings. Several non-invasive methods by portable equipment, including XRF, mid- and near-FTIR, UV-Vis and Raman spectroscopy, as well as XRD, are discussed in detail along with their impact on our understanding of painting materials and execution techniques. Examples of successful applications are given, both for point analyses and hyperspectral imaging approaches. Lines for future perspectives are finally drawn.

Chromatographic and spectroscopic identification and recognition of ammoniacal cochineal dyes and pigments.

In this work a combined chromatographic and spectroscopic approach is used to provide a diagnostic assessment of semi-synthetic ammoniacal cochineal through the syntheses of its dyes and lakes according to art historical recipes. Commercially introduced in the late XIX century as a dye and pigment, it was used to obtain a brilliant purplish/violet nuance which provided a more stable option over carminic acid although its evidenced use in manufacts and artworks of heritage importance have been scarcely documented. Through HPLC-DAD, it has been possible to identify 4-aminocarminic acid as the main component of ammoniacal cochineal highlighting a chemical formula analogous to acid stable carmine, a recent patented food dye. FTIR clearly distinguishes the amine group in the ammoniacal cochineal dye preparation and TLC-SERS allows for an adequate separation and spectral differentiation in its main components to be evidenced. Colloidal SERS has permitted spectral markers useful in discerning ammoniacal cochineal over carminic acid to be highlighted and discussed. Finally, the methods experimented in this study for the identification of ammoniacal cochineal have been validated on analyzing a sample of dyed wool.

A non-invasive NMR relaxometric characterization of the cyclododecane-solvent system inside porous substrates.

With the aim of deepening the knowledge on the behavior of cyclododecane (CDD) as a temporary consolidant agent for weathered stones, NMR longitudinal and transverse relaxation decays have been exploited to follow the distribution of cyclododecane solutions into porous matrices. By measuring as function of time the relaxation decay constants of CDD solutions dropped onto porous supports, it has been possible to differentiate the step encompassing the solvent evaporation, which determines the consolidant migration within the matrix, from that governing the consolidant sublimation, which is related to the consolidation effectiveness over time.

A vibrational spectroscopic and principal component analysis of triarylmethane dyes by comparative laboratory and portable instrumentation.

This contribution examines the utility of vibrational spectroscopy by bench and portable Raman/surface enhanced Raman and infrared methods for the investigation of ten early triarlymethane dye powder references and dye solutions applied on paper. The complementary information afforded by the techniques is shown to play a key role in the identification of specific spectral marker ranges to distiguish early synthetic dyes of art-historical interest through the elaboration of an in-house database of modern organic dyes. Chemometric analysis has permitted a separation of data by the discrimination of di-phenyl-naphthalenes and triphenylmethanes (di-amino and tri-amino derivatives). This work serves as a prelude to the validation of a non-invasive working method for in situ characterization of these synthetic dyes through a careful comparison of respective strengths and limitations of each portable technique.

The Book of Kells: a non-invasive MOLAB investigation by complementary spectroscopic techniques.

This paper highlights the efficacy of non-invasive portable spectroscopy for assessing the execution technique and constituent materials in one of the most important medieval manuscripts, the Book of Kells. An aimed campaign of in situ measurements by the MObile LABoratory (MOLAB) has analyzed its elemental composition and vibrational and electronic molecular properties. The ample analytical toolbox has afforded complementary diagnostic information of the pigment palette permitting the characterization of both inorganic and organic materials as pigments and dyes in the white, purple, blue, red, orange, green and black areas. In particular, the novel widespread use of calcinated gypsum (anhydrite) as both a white pigment and in correlation to the organic dyes in this manuscript has been noted. The non-invasive identification of the organic dye orchil is significant considering its rare non invasive detection in medieval manuscripts. Finally the occurrence of particular alterations of the organic black areas giving rise to calcium carboxylate and calcium oxalate has been specifically highlighted. Importantly, this work elaborates complex aspects of the employed painting materials which have given rise to numerous significant points of interest for a more elaborate understanding of this Irish treasure.

A randomized clinical trial to compare the Goshgarian and Nance palatal arch.

The aim of this trial was to evaluate whether a Nance or Goshgarian palatal arch was most effective for prevention of mesial drift, distal tipping, prevention of mesio-palatal rotation of the upper first permanent molars, and patient comfort and ease of removal. Patients were recruited from a district general hospital and a specialist orthodontic practice and randomly allocated to a Goshgarian (n = 29) or a Nance (n = 28) group. Pre-treatment study models (T1) were taken followed by the placement of the palatal arch, premolar extractions, and upper and lower fixed appliances. The clinical end point was 6 months (T2), at which time, an impression for an upper study model was taken. The amount of upper first permanent molar mesial movement, distal tipping, and mesio-palatal rotation was measured by scanning T1 and T2 study models and then using a software program to calculate molar changes. In addition, the patients recorded their discomfort scores using a seven-point Likert scale at each recall visit. Forty-nine patients (86 per cent) completed the trial. t-tests were used to compare molar movements between the Goshgarian and Nance palatal arch groups. There were no statistically significant differences between the palatal arches in terms of prevention of mesial drift or distal tipping (P > 0.05). There was a statistically significant difference in the amount of molar rotation between the arch types, with both exhibiting some disto-palatal rotation even though they were not activated for this movement. The Goshgarian palatal arch produced marginally more disto-palatal rotation than the Nance arch (P = 0.02), although this may not be considered clinically significant. A Mann-Whitney test revealed that there was also a statistically significant difference in pain scores between the Goshgarian and the Nance arch, with the latter being associated with more discomfort (P = 0.001). This trial did not support any preference in the use of the Goshgarian or Nance palatal arch, unless the slightly reduced patient discomfort with the Goshgarian arch is considered significant.

Anxiolytic effects of lavender oil inhalation on open-field behaviour in rats.

To establish a valid animal model of the effects of olfactory stimuli on anxiety, a series of experiments was conducted using rats in an open-field test. Throughout, effects of lavender oil were compared with the effects of chlordiazepoxide (CDP), as a reference anxiolytic with well-known effects on open-field behaviour. Rats were exposed to lavender oil (0.1-1.0 ml) for 30 min (Experiment 1) or 1h (Experiment 2) prior to open-field test and in the open field or injected with CDP (10 mg/kg i.p.). CDP had predicted effects on behaviour, and the higher doses of lavender oil had some effects on behaviour similar to those of CDP. In Experiment 3, various combinations of pre-exposure times and amounts of lavender oil were used. With sufficient exposure time and quantity of lavender the same effects were obtained as in Experiment 2. Experiment 4 demonstrated that these behavioural effects of lavender could be obtained following pre-exposure, even if no oil was present in the open-field test. In Experiments 2-4, lavender oil increased immobility. Together, these experiments suggest that lavender oil does have anxiolytic effects in the open field, but that a sedative effect can also occur at the highest doses.

High-energy cutoff in the spectrum of strong-field nonsequential double ionization.

Electron energy distributions of singly and doubly ionized helium in an intense 390 nm laser field have been measured at two intensities (0.8 PW/cm2 and 1.1 PW/cm2, where PW is defined as 10(15) W/cm2). Numerical solutions of the full-dimensional time-dependent helium Schrödinger equation show excellent agreement with the experimental measurements. The high-energy portion of the two-electron energy distributions reveals an unexpected 5U(p) cutoff for the double ionization (DI) process and leads to a proposed model for DI below the quasiclassical threshold.

Three days of pivmecillinam or norfloxacin for treatment of acute uncomplicated urinary infection in women.

Pivmecillinam is a unique beta-lactam antimicrobial that has been used for the treatment of acute uncomplicated urinary infection for > 20 y. Since this agent was introduced, the quinolone antimicrobials have become widely used for the same indication. This study compared the efficacy of a 3-d regimen of pivmecillinam 400 mg b.i.d. with norfloxacin 400 mg b.i.d. Women aged between 18 and 65 y presenting with symptoms of acute cystitis of < 7 d duration were eligible for enrollment; 483 were randomized to receive pivmecillinam and 471 to receive norfloxacin. In each group, 30% of women had negative urine cultures prior to therapy. Bacteriologic cure at early post-therapy follow-up was achieved in 222/298 (75%) pivmecillinam patients and 276/302 (91%) norfloxacin patients [p < 0.001; 95% confidence interval (CI) 12.0-21.8]. Clinical cure/improvement at Day 4 following initiation of therapy was observed in 434/457 (95%) women who received pivmecillinam and 425/442 (96%) who received norfloxacin (p = 0.39; 95% CI 1.5-3.9). Early post-therapy (11 +/- 2 d) clinical cure was achieved in 360/437 women (82%) who received pivmecillinam and 381/433 (88%) who received norfloxacin (p = 0.019; 95% CI 0.9-10.3). In women aged < or = 50 y, early clinical cure rates were 294/351 (84%) for pivmecillinam and 299/340 (88%) for norfloxacin (p = 0.11; 95% CI 1.0-9.4). Adverse effects were similar for both regimens, and there was no evidence of the emergence of organisms of increasing resistance with therapy. Short-course therapy with norfloxacin was superior to that with pivmecillinam in terms of bacteriologic outcome, although differences in clinical outcome were less marked. In conclusion, short-course therapy with pivmecillinam is an effective empirical treatment for pre-menopausal women.

Health needs assessment in intermediate care of elderly people.

The National Service Framework for older people (Department of Health (DOH), 2001a) identifies health promotion as one of the eight standards for improving the health and well-being of older people. Population health needs assessment is the first stage in any public health promotion cycle. This article critiques health needs assessment methodology, investigates the origins of health needs assessment and discusses the application of health needs assessment theory in a community hospital setting.

Treatment of acute exacerbations of chronic bronchitis: comparison of trovafloxacin and amoxicillin in a multicentre, double-blind, double-dummy study. Trovafloxacin Bronchitis Study Group.

The efficacy and safety of trovafloxacin and amoxicillin were compared in a double-blind, double-dummy multicentre trial involving 412 patients (> or = 40 years of age) with acute exacerbations of chronic bronchitis (AECBs). Patients were randomized to 5 days' oral treatment with 200 or 100 mg trovafloxacin administered once daily, or 500 mg amoxicillin given three times daily. Overall clinical efficacy at the end of therapy was similar in each treatment group, with clinical success (cure+improvement) achieved in 88% and 91% of clinically evaluable patients receiving trovafloxacin 200 mg and 100 mg, respectively, and in 89% of amoxicillin-treated patients. Corresponding rates at follow-up were 77%, 85% and 79%, respectively. Similar responses were noted at the end of treatment and end of study in the intent-to-treat patients. Although all three treatments produced similar bacteriological efficacy, there was a trend towards higher eradication rates for Haemophilus influenzae among patients (both clinically evaluable and intent-to-treat populations) treated with trovafloxacin 200 mg compared with those treated with amoxicillin. Both drugs were well tolerated, with treatment-related adverse events, of which headache and gastrointestinal disturbances were the most common, occurring in 12% and 6% of patients in the trovafloxacin 200 mg and 100 mg groups, respectively, and in 9% of amoxicillin-treated patients.

A biomechanical study of Jefferson fractures.

STUDY DESIGN: Fifteen specimens of the first cervical vertebra were tested by the application of pure tensile forces to failure. Seven specimens had intact transverse ligaments, and eight had transection of the transverse ligament before testing. Specimens were tested to failure by the rapid application of laterally directed tensile force to the ring; this force then was exerted through the lateral masses to simulate the mechanism of injury for this fracture as proposed by Jefferson. OBJECTIVES: To measure the biomechanical characteristics of the C1 ring, including the fracture patterns created with tensile loading, and to describe the influence of the transverse ligament on the behavior of the ring as it failed under tension. SUMMARY OF BACKGROUND DATA: Jefferson fractures have been reproduced in the laboratory by subjecting head and neck preparations to axial load. However, no previous detailed biomechanical studies of the fracture characteristics of the isolated C1 vertebra have been reported. METHODS: Specimens were tested to failure by rapid application of laterally directed tensile forces to the ring. RESULTS: Eleven two-part and three three-part fractures occurred. The mean tensile strength of the atlas was found to be 2,280 N. The average deformation required to fracture the C1 ring was 1.57 mm. The total energy absorbed by the ring averaged 1.99 N-m. There was no statistically difference between those specimens with the transverse ligament intact and those without a transverse ligament. CONCLUSIONS: The results of this study show that fractures of the C1 ring of greater than two parts can occur with pure tensile loading. The ring will fracture with as little as 1 mm of deformation.

A biomechanical study of anterior thoracolumbar screw fixation.

STUDY DESIGN: The pullout strength of unicortical and bicortical screws in thoracic and lumbar vertebral bodies was measured as a function of bone mineral density. OBJECTIVES: To determine the influence of bone mineral density and screw insertion technique on the stability of anterior thoracolumbar spine screw fixation. SUMMARY OF BACKGROUND DATA: No previous study has addressed the specific technique of screw insertion or stability of screw fixation in the anterior spine. METHODS: Fifty-one human thoracic vertebral bodies were tested in pullout with 6.55-mm cancellous screws inserted using unicortical and bicortical techniques. RESULTS: Pullout force increased exponentially with increasing bone mineral density for unicortical and bicortical screws. Bicortical screws were significantly stronger in resisting pullout than unicortical screws. CONCLUSION: Advancing an anterior vertebral body screw to engage the second cortex increases resistance to pullout by 25-44%, depending on vertebral bone mineral density. The difference in resistance between unicortical and bicortical techniques was smaller in specimens with low mineral densities.

Quantitative anatomy of the occiput and the biomechanics of occipital screw fixation.

STUDY DESIGN: The surgically relevant osseous anatomy of the human anatomy was carefully studied and described. The stability of cortical and cancellous screws placed in anatomic sites commonly used for internal fixation of the occiput was tested. OBJECTIVES: To define the bony anatomy of the occiput in quantitative terms and to measure the ability of cortical and cancellous screws inserted at sites commonly used for internal fixation. SUMMARY OF BACKGROUND DATA: To the authors' knowledge, no previous studies described the gross anatomy of the occiput in specific relation to the internal venous structures in the cranium and to the biomechanical strength of screw fixation in different areas of the occiput. METHODS: Thirty-seven human occiputs were carefully measured using calipers. Thin sections from six such specimens were analyzed with specific attention to cortical thicknesses. Stability of screws placed in various locations in the occiput were tested in axial pullout. RESULTS: The thickness of the occiput varied from extremely thin to a 0.1-mm thickness in the region of the cerebellar fossa and increased to a maximum of 8.3 mm at the level of the superior nuchal line and at the transverse sulcus. Results of pullout testing showed that the cancellous screws were as strong as the cortical screws in this area. In areas of the occiput thicker than 7 mm, unicortical fixation was as strong as bicortical fixation. CONCLUSION: There is a wide variation in thickness of the bone of the occiput. The strength of screw fixation was proportional to the bone's thickness.

Morphologic study of lumbar vertebral osteophytes.

BACKGROUND: Vertebral osteophytes are one of the principal radiographic diagnostic criteria for degenerative change in the lumbar spine. These osteophytes have been previously classified by morphologic features into two groups, the "traction spur" and the "claw spur." It has been stated that the traction spur is a sign of spinal instability. METHODS: Lumbar spines from 20 cadavers provided 120 vertebrae from T-11 to L-5 and 240 vertebral rims for study. The presence of osteophytes was determined by measurement with digital calipers. The type of osteophyte was then determined visually, using the Macnab classification. RESULTS: Sixty vertebral rims were found to have significant osteophytes. Twenty-four vertebral rims had osteophytes of the claw type only, and 11 had osteophytes of the traction type only. Of the eight vertebrae with traction osteophytes alone and with the adjacent vertebra available for study, none had such a corresponding osteophyte. CONCLUSION: Traction spurs and claw spurs frequently coexist on the same vertebral rim. This suggests that they may result from the same degenerative process and do not necessarily reflect the results of two distinct pathologic processes.

Randomized, multicentre study of the efficacy and tolerance of azithromycin versus clarithromycin in the treatment of adults with mild to moderate community-acquired pneumonia. Azithromycin Study Group.

Adults with mild to moderate community-acquired pneumonia were treated with azithromycin (500 mg once daily for 3 days) or clarithromycin (250 mg twice daily for 10 days) and clinically assessed between days 3 and 7 and days 12 and 16. Patients classified as improved at the day 12-16 visit were also evaluated between days 19 and 23. Two hundred three patients were treated (101 with azithromycin, 102 with clarithromycin). A satisfactory clinical response was recorded at the end of therapy in 83 of 88 (94%) evaluable azithromycin-treated and 84 of 88 (95%) evaluable clarithromycin-treated patients (P=0.518). At day 19-23, only one patient in each treatment group had relapsed. Thirty-one of 32 (97%) pathogens isolated from patients in the azithromycin group were eradicated, compared with 32 of 35 (91%) isolated from clarithromycin patients. In all patients with atypical pneumonia, the clinical response was satisfactory at follow-up. Incidences of treatment-related adverse events were similar for the two groups (P=0.815). Two (2%) clarithromycin patients discontinued therapy due to severe treatment-related adverse events; none in the azithromycin group did. This study shows that a 3-day, once-daily course of azithromycin is as clinically effective and well tolerated as a 10-day, twice-daily course of clarithromycin in the treatment of mild to moderate community-acquired pneumonia.

The trabecular anatomy of thoracolumbar vertebrae: implications for burst fractures.

The gross osseous anatomy of the spine has been the subject of much study but the internal architecture and trabecular anatomy of thoracolumbar vertebrate has not previously been well described. This study is based on high resolution x-ray images of 56 isolated thoracolumbar vertebrae and thick sections obtained from them. A previously undescribed array of trabeculae was documented which originated from the medial corner of the base of the pedicles and extended in a radial array throughout the vertebral body. This trabecular array persisted even in severely osteoporotic specimens. The cortex of the vertebral canal thinned abruptly near the base of the pedicle creating what may be a stress concentration at this site. This corresponded to the site of origin of the trabecular array. The presence of this possible stress concentration, in proximity to the trabecular array, may provide an explanation for the trapezoidal shape of the bony fragments that are frequently retropulsed into the spinal canal in axial load type burst fractures, common in this area of the spine.

Steady-state auditory evoked responses to pulsed frequency modulations in children.

This study investigated steady-state auditory evoked responses to pulsed frequency modulations (FM) of a continuous tone in normal children ranging in age from 6 to 12 years. We examined variations in response amplitude and phase as a function of age, recording site, and FM pulse duration. The surface topography of these evoked potentials suggested a relatively broad distribution with maximal responses observed at frontal electrode sites, smaller responses from parietal leads and the smallest responses were evident at the temporal lobe placements. Response parameters varied significantly as a function of pulse duration. Fifty milliseconds pulses elicited responses that were on average 20% larger than 100 ms FM pulses. Mean phase differences suggested that responses to the 100 ms pulses also lagged behind responses to the 50 ms pulses by the equivalent of 20 ms. There were no significant age-related variations in response amplitude. Phase varied with age only in response to the 50 ms FM pulses. The findings indicated that steady-state responses are sensitive to temporal parameters of frequency change present in pulsed modulations. The possibility is raised that this paradigm may be clinically useful in detecting dysfunction of specialized auditory mechanisms involved in frequency modulation analysis.

Randomized, double-blind, comparative study of grepafloxacin and amoxycillin in the treatment of patients with community-acquired pneumonia.

This randomized, multicentre, double-blind, double-dummy study assessed the efficacy and safety of 7 or 10 day regimens of grepafloxacin, 600 mg od, compared with amoxycillin, 500 mg tds, in the treatment of community-acquired pneumonia (CAP). A total of 264 patients were recruited at 43 centres (127 received grepafloxacin and 137 received amoxycillin), of whom 207 patients (78%) completed the study. Clinical and microbiological efficacy were assessed at the end-of-treatment visit (3-5 days after the last dose) and at the follow-up visit (28-42 days after the last dose). At follow-up, patients in the evaluable population treated with grepafloxacin demonstrated a clinical response rate (76%; 87/114) equivalent to that seen with amoxycillin (74%, 85/111, 95% CI = -12%, 10%) while, in the intent-to-treat population with a documented bacterial pathogen, the clinical success rate in the grepafloxacin group (78%, 29/37) was significantly higher than in the amoxycillin group (58%, 28/48), 95% CI = 2%, 43%). In patients from the evaluable population in whom the pathogens were documented the clinical success rate favoured grepafloxacin, compared with amoxycillin (79%, 26/33 versus 63%, 26/42, respectively; 95% CI = -5.2%, 38.1%). Microbiological eradication with grepafloxacin was statistically superior to amoxycillin in the evaluable population; the success rate was 89% (32/36) in the grepafloxacin group compared with 71% (32/45) for the amoxycillin group (95% CI = 2%, 37%). The pathogens most commonly isolated from patients were Haemophilus influenzae, Moraxella catarrhalis and Streptococcus pneumoniae. The success rates for infections caused by S. pneumoniae and H. influenzae at follow-up were higher with grepafloxacin than with amoxycillin. Grepafloxacin was well tolerated, with a safety profile comparable to that of amoxycillin. The therapeutic judgement of patients and investigators at the patient's last visit, as well as the assessment of individual respiratory signs and symptoms, yielded comparable results with both treatments. The results of this study indicate that grepafloxacin, 600 mg od for 7-10 days, is equivalent to or better than amoxycillin, 500 mg tds for 7-10 days in achieving a successful clinical and microbiological response in the treatment of patients with CAP.