Theoretical study on oligothiophene N-succinimidyl esters: size and push-pull effects.

We report a theoretical study on the optical properties of bithiophene and terthiophene N-succinimidyl esters, which have been functionalized with a methylsulfanyl group in the alpha or the beta positions. Time-dependent density functional theory (TD-DFT) and approximate coupled-cluster singles and doubles with the resolution of identity technique (RI-CC2) calculations have been performed in the ground and excited states. The RI-CC2 results for absorption and fluorescence energies are in better qualitative agreement with experiments, whereas TD-DFT does not correctly describe the higher energy part of the absorption spectra of beta-substituted bithiophenes, due to the presence of charge-transfer states. Systems functionalized at the alpha position show a large red-shift of the main absorption and fluorescence band and a larger Stokes-shift compared to the unsubstituted species. These effects are in most cases less pronounced for the beta-substituted structures. In particular, we found that the Stokes-shift of the alpha-substituted structures is larger than the one of the beta-substituted species due to a more planar orientation of the methylsulfanyl group with respect to the neighbouring thiophene in the excited state.

Solution-phase microwave-assisted synthesis of unsubstituted and modified alpha-quinque- and sexithiophenes.

The facile synthesis of poorly soluble unsubstituted and modified alpha-quinque- and sexithiophenes under microwave irradiation in the liquid phase is described. The use of microwave irradiation allowed these compounds to be prepared in a few minutes and at high yields by means of the Suzuki cross-coupling reaction. Unsubstituted sexithiophene was obtained in 10 min via the one-pot borylation/Suzuki reaction, purified according to a very simple procedure, and isolated in 84% yield. The efficient synthesis of two new methylated quinque- and sexithiophenes displaying liquid crystalline properties is reported. A new microwave-assisted methodology for the conversion of aldehyde-terminated quinque- and sexithiophenes into the corresponding cyano derivatives is also described. The use of microwaves was extended to the Sonogashira coupling reaction and found to be very effective in the preparation of a quinquethiophene containing acetylenic spacers. The electronic and optical characterization of this compound is reported and discussed in relation to that of unsubstituted quinquethiophene.

Oligothiophene isothiocyanates as a new class of fluorescent markers for biopolymers.

The regioselective synthesis of fluorescent oligothiophene isothiocyanates is described. The isothiocyanates were reacted with bovine serum albumin (BSA) following standard procedures and the optical properties of the oligothiophene-BSA conjugates were analyzed as a function of oligomer concentration, time, and irradiation power. The oligothiophene-BSA conjugates were chemically very stable and their photoluminescence characteristics persisted unaltered for several months. Photoluminescence data relative to the conjugate of an oligothiophene-S,S-dioxide isothiocyanate with monoclonal anti-CD8 antibody are reported. No fluorescence quenching was observed following the binding of the isothiocyanate to the antibody and the conjugate displayed high chemical stability and photostability.

[Correlation between computed tomography and isokinesis in patients with reconstructive surgery of anterior cruciate ligament of the knee]. / Correlazione fra tomografia computerizzata e isocinesi in pazienti operati diricostruzione di ricostruzione di legamento crociato anteriore di ginocchio.

AIM: The aim of this study was to correlate the length (measured by computed tomography) of the anterior cruciate neoligament following knee surgery with the time required by the flexors-extensors of the knee to reach isokinesis (measured using an isokinetic method). MATERIAL AND METHODS: Twenty-five patients (all males, median age 25.4 years), who had undergone surgical repair of the anterior cruciate ligament (ACL), were assessed by computed axial tomography (CT) and isokinetic tests a mean of 6.3 months after their operation. The following isokinetic parameters were calculated: time to reach isokinesis in flexion, time to reach isokinesis in extension, flexion strength, and extension strength. Mean values were calculated from all the values recorded during the test cycles performed. The CT examinations, after lateral scanograms, were carried out with 1 mm contiguous axial scans parallel to the tibial plate. It was possible to assess the integrity of the neoligament which was measured from a section of the tibial plate above the tibial cartilage to its insertion in the intercondylar furrow. RESULTS: As expected, all the values recorded from the healthy knee were significantly different from those recorded on the operated side. As far as concerns analysis of any correlations, there were good correlations between the time to reach isokinesis in extension and the length of the ACL both on the operated side (r=.62) and the healthy side (r=.69), whereas the correlations between the length of the ACL and all other measurements were moderate or very weak (from 0.44 to 0.03). DISCUSSION AND CONCLUSIONS: That the isokinetic measurements show an increased time for the extensor muscles of the operated knee to reach isokinesis is related to altered biomechanics of the passage of the tibia from a posterior translaction position to one of an anterior translaction that is, to anterior displacement of the tibia during extension of the knee, which leads to the prolonged time. The correlation between this time and the length of the ACL, as measured by CT, offers the possibility of being able to monitor the outcome of cruciate ligament repair periodically during various phases of rehabilitation treatment and of only using control CT examinations if there are any complications and/or problems.

[Behavior of Helicobacter pylori in 3d and 4th age-bracket patients]. / Comportamento di Helicobacter pylori in pazienti della III e IV età.

AIMS AND BACKGROUND: Helicobacter pylori is known to be the pathogenic agent of atrophic gastritis and above all ulcer disease. It is also thought to play a role, together with other factors, in the development of stomach cancer and is currently the focus of numerous studies. In industrialised countries, infection is relatively commonplace in children, whereas its incidence rises more steeply in patients aged over 35, reaching a mean prevalence of 50% in over 60 year olds. METHODS: During 1997 the authors carried out an epidemiological study to assay levels of anti-Helicobacter pylori (IgG anti-Hp) in a sample of 91 aged patients hospitalised in the S. Margherita Geriatric Hospital in Pavia. The patients had been admitted to hospital for various pathologies and the study also took into account gastric pathologies which usually, particularly in neoplastic forms, prefers the third and fourth ages. The assay for antibodies was performed using mouse monoclonal antibody, specific for Helicobacter pylori, absorbed on a polyester pad. A total of 5 ml of blood were collected from each patient. The blood samples were all centrifuged and the serum frozen at -20 degrees C until the tests were performed. RESULTS: In this study, 46 of the 91 patients tested were positive for anti-Helicobacter pylori antibodies, 35 were negative and 10 borderline. CONCLUSIONS: The high level of positive results found in these patients is in line with the findings reported by other authors.

[The quality of life of the geriatric patient after a surgical intervention. VI. Interventions on the biliary tract]. / Qualità di vita del paziente geriatrico dopo intervento chirurgico. Nota VI: interventi sulle vie biliari.

After reviewing the literature on this subject, the authors examine the quality of life of geriatric patients after biliary tract surgery secondary to biliary tract carcinoma or non-neoplastic pathologies. From an analysis of the results the authors conclude that surgery is useful not only in non-neoplastic forms, but also in the event of carcinoma given that it is possible to improve the quality of life of these patients.

[Intestinal infarct in a geriatric patient]. / Infarto intestinale nel paziente geriatrico.

INTRODUCTION AND METHODS: After reviewing the literature on the subject, the authors analysed the patients suffering from intestinal infarction selected from those examined between 1-1-1985 and 31-12-1995. It was found that out of 11,500 patients only 9 (0.07%) suffered from this pathology. RESULTS: The authors found that geriatrics (between 65 and 74 years old) were most commonly affected by this pathology, with a majority of females (55.35%) and that the most frequently associated pathologies were cardiopathies. Medical treatment and surgery were used (depending on the results of the various tests). Of these patients only 3 (33.32%) were treated medically, whereas the remainder underwent surgery using different techniques in each case. Excision of the thrombus was performed in 22.23% with the partial resection of the intestine in 44.45%. The quality of life in operated patients was reasonably satisfactory. Those undergoing excision of the thrombus enjoyed 100% wellbeing compared to only 25% of those undergoing partial intestinal resection. Those receiving medical treatment all died. The most frequent complications were short intestine (11.11%) and wound infection with possible dehiscence. CONCLUSIONS: The authors conclude by highlighting the gravity of the pathology from a diagnostic and therapeutic point of view and by underlining that the quality of life in general of operated patients was good in 33.34% of those living, with Karnofsky's Index of 100 in 22.23%.

[Arterial aneurysms in geriatric age]. / Gli aneurismi arteriosi nell'età geriatrica.

After reviewing the literature on the subject, the authors examine all the cases of aortic aneurysm referred to their attention. From the tests performed, they note that males are most often affected and the age group with the highest incidence is the seventh decade of life, in particular between 60-66 years old. After having observed a pulsing abdominal mass leading to a suspected diagnosis, the radiological methods recommended by the authors include echotomography or CT, or if required, magnetic resonance. Arteriography is less convincing than the previous tests for diagnostic purposes because, as well as providing a false image of the vessel lumen (owing to the overlay of stratified thrombi it can show a virtually normal lumen), it may cause a risk of embolism. The surgeon therefore prefers an intraoperative finding in the case of subrenal aneurysm. In conclusion, faced with a diagnosis of aneurysm of the abdominal aorta, in the majority of cases, having prepared the patient, it is necessary to perform aorto-bisiliac or bifemoral graft surgery depending on aneurysm size as soon as possible in order to avoid the fissuration or even the rupture of the aneurysm.

[Quality of life of geriatric patients after surgery. VII. Lung tumors]. / Qualità di vita del paziente geriatrico dopo intervento chirurgico. Nota VII: Tumori del polmone.

After reviewing the literature on this subject, the authors examine the results of a five-year follow-up in all patients undergoing lung cancer surgery. The results obtained showed that old-age patients (third age) are more numerous than geriatric (fourth age) patients, and males are more frequently affected than females. The most frequent localisation in the series examined was the upper right lobe and the majority of these patients underwent lobectomy, the form of surgery that produced the best results (30.3% alive and well with a Karnofski index as high as 90 in some cases). The authors conclude that when the patient's conditions allow, surgery is advisable in lung cancer in an attempt to improve the patient's quality of life.

[Quality of life in geriatric patients after surgery. Note V. Pancreatic surgery]. / Qualità di Vita del paziente geriatrico dopo intervento chirurgico. Nota V. Interventi sul pancreas.

After a brief review of the literature on this topic, the authors examine the Quality of Life in patients undergoing surgery for neoplasia of the pancreas. They found that radical pancreatic surgery for cancer in elderly patients produced better results than hepatic surgery, even if the death rate was again very high (45.95%). It is very important to underline that the patient's general conditions are very important in this form of surgery. They provide the basis for selecting derivative, endoscopic or percutaneous surgery, with the possible application of an endoprosthesis so as to treat jaundice and improve the patient's Quality of Life.

[Gastric lymphomas in old age]. / I linfomi gastrici dell'età geriatrica.

After having examined the literature on the subject, the authors examined 23 cases of lymphoma selected from those admitted to hospital over the past 10 years: 44.78% were Hodgkin and 65.22% non-Hodgkin. They examined the localisation, which was gastric in all cases, associated pathologies and treatment, which was total gastrectomy in 56.52%. Moreover, the authors also considered the quality of life of patients undergoing total gastrectomy which was found to be good in 23.07%, a percentage which is higher than that expressed for other types of surgery (gastric resection) or medical treatment (chemotherapy). In conclusion, the authors affirm that total gastrectomy is worth performing in these patients, even if the percentage of deaths is higher than for gastric resection, given that te quality of life is better in total gastrectomy.

Polyhydroxyoligothiophenes. 2. Hydrogen-Bonding-Oriented Solid State Conformation of 3,3'-Bis(2-hydroxyethyl)-2,2'-bithiophene and Regioselective Synthesis of the Corresponding Head-to-Head/Tail-to-Tail Quater- and Sexithiophene.

This paper reports the X-ray structure of 3,3'-bis(2-hydroxyethyl)-2,2'-bithiophene (1), which is the building block for the synthesis of head-to-head/tail-to-tail 2-hydroxyethyl-substituted oligothiophenes. Contrary to all the bithiophenes reported so far, 1 exhibits a noncoplanar anti conformation and an inter-ring twist angle (67.5 degrees ) which is the largest ever measured for adjacent rings of alpha-conjugated oligothiophenes. This unusual conformation appears to be dictated by intermolecular hydrogen-bonding interactions involving the OH groups, which bind the molecule in close packed layers. The paper also describes the regioselective synthesis of the dimer and the trimer of 1, namely of 3,3',4",3"'-tetrakis(2-hydroxyethyl)-2,2':5',2":5",2"'-quaterthiophene (3c) and of 3,3',4",3"',4"",3""'-hexakis(2-hydroxyethyl)-2,2':5',2":5",2"':5"',2"":5"",2""'-sexithiophene (4b). 3c And 4b were obtained through palladium(0)-catalyzed coupling of the mono- and distannanes of the tetrahydropyranyl derivative of 1 with the appropriate monobromo compound (Stille's reaction). Finally, the paper reports force-field calculations which suggest that the low lambda(max) values measured for 1, 3c, and 4b are also the result of intramolecular hydrogen-bonding interactions which favor highly twisted conformations in solution.

[Quality of life of the aged after surgery. 3. Hepatic carcinoma]. / Qualità della vita nel vecchio dopo intervento chirurgico. Nota III--Carcinoma epatico.

Following a review of the literature on this topic, the authors examine the quality of life in elderly patients who have undergone hepatic resection due to carcinoma in the past 5 years. An analysis of the results obtained showed that there was 20% wellbeing in right hepatectomized patients, only 14.29% in left hepatectomized and bisegmentectomized patients, and 11.11% in patients who had undergone the excision of metastases. In conclusion, the authors affirm that even if the number of deaths in relatively high it is always worth operating in an attempt to improve the patient's quality of life.

[Quality of life in the aged after surgery. IV. Pathology of the esophagus]. / Qualità della vita nel vecchio dopo intervento chirurgico-Nota. IV: Patologia dell'esofago.

Following a careful examination of the literature on the subject, the authors examine the follow-up records of all patients operated over the past 10 years for non-neoplastic and neoplastic esophageal pathologies. From the results it emerged that all those operated for non-neoplastic pathologies were still living and their quality of life was good with a very high proportion of patients presenting a score of 100 for Karnofsky's index. With regard to neoplastic forms, on the other hand, many patients had died (approximately 50%), but the majority of those living, who had undergone gastro-esophageal resection and consequent esophago-gastrostomy with thoracization of the stomach, were well with a Karnofsky score of 100. The authors explain these results by taking into account the general conditions (biological age) of patients and conclude that surgery is advisable in both non-neoplastic and neoplastic forms, given that it is important to try to improve the quality of life even in the latter.

[The quality of life of the elderly after a surgical intervention. II. Gastric carcinoma]. / Qualità di vita del vecchio dopo intervento chirurgico. Nota II--Carcinoma gastrico.

Having reviewed the literature on this topic, the authors examined the "quality of life" of elderly patients undergoing surgery for gastric carcinoma over the past 5 years. From the results obtained it was seen that the most frequent operation was total gastrectomy (51.1%), followed by gastric resection (48.9%); it was therefore possible to assert that living patients were all well, with a score of 100 on Karnofsky's scale (22.40%), despite the high percentage of deaths during the period examined. The authors therefore concluded that, given that the "quality of life" of those undergoing surgery was satisfactory, it is worthwhile operating whenever possible to give geriatric patients the possibility of leading a normal life.

[Tumors of the breast in old age]. / I tumori della mammella nell'età geriatrica.

After reviewing the literature on this topic the authors studied all patients admitted to the Institute of Surgical Pathology I at the University of Pavia for breast cancer between 1-1-1974. An analysis of the findings revealed that: (a) Out of 993 patients with breast cancer, 204 (20.54%) belonged to the geriatric age group (> 65 years old) and of the latter 135 (66.17%) belonged to the 3rd age group and 69 (33.82%) belonged to the 4th age group (> 75 years old). (b) In the 3rd age group 25 (18.51%) were benign tumours and 110 (81.48%) were malignant, whereas in the 4th age group 4 (5.79%) were benign and 65 (94.20%) were malignant. (c) Familial patterns were also examined and were found to be positive in 47 (23.03%) cases in the 3rd age group and in 30 (14.71%) in the 4th age group. (d) In the physiological anamnesis it is interesting to note that there was 1 menarche before 12 (0.9%) in the 3rd age group; delayed menopause (after 50) in 66 cases (60%) in the 3 rd age group and in 29 cases (44.61%) in the 4 th age group. (e) In the pathological anamnesis of the patients in question it was observed that the most frequent site of previous tumours was the breast (72 cases, equivalent to 10.9% in the 3rd age group; 9 cases, 13.8% in the 4th age group). (f) In the next pathological anamnesis and at EOL it was observed that the tumours was most often found in the supero-external quadrant, in the right breast in the 3rd age group (66 cases, 48.89%) and in the left one in the 4th age group (42 cases, 60.87%). (g) Test included breast cancer scan, mammography, aspirated needle and biopsy where required. (h) Surgery in the form of Halsted's mastectomy was the preferred therapy and as early as possible. Some Authors use conservative therapy. (i) Histological tests were performed in all patients and revealed that the most frequent malignant tumour was ductal carcinoma. (j) Postoperative complications took the form of wound suppuration. (k) Only one tumour (carcinoma) was observed in male patient aged 83 years old, without metastasis. From the above findings it can be concluded that the most evident risk factor for breast cancer is the influence of the estrogen hormone.

[The quality of life of the elderly patient after a surgical intervention. I. Interventions on the colon]. / Qualità di vita del vecchio dopo intervento chirurgico. Nota I--Interventi sul colon.

Following a brief review of the literature on this topic, the paper analyses a series of geriatric undergoing surgery for cancer of the large intestine and controlled during follow-up over the past years. From the results obtained, the authors assessed the quality of life of these patients according to Masera and Esposito's classification, as a state of well-being, intermediate or illness: it was found that 78.7% were in a state of well-being, 10.3% were unchanged, 12.1% were in a state of illness, and only 6.9% had died. The authors therefore concluded that the quality of life in the majority of elderly patients undergoing surgery is good, thus encouraging surgeons to intervene.

[Intestinal occlusions in the elderly patient]. / Occlusioni intestinali nell'anziano.

After reviewing the literature on this topic, the authors examine all patients admitted to the Institute of Surgical Pathology in Pavia with a diagnosis of intestinal occlusion from 1-1-1974 to 31-12-1990. Of these, only those aged over 65 were included in the study and were in turn subdivided into 3rd and 4th age groups. The etiopathogenesis of this disorder is also discussed, stressing that it may be non-neoplastic (Group I) or neoplastic (Group II). The treatment used is also examined (surgical in the majority of cases) together with postoperative complications occurring in these patients. From the results obtained it is concluded that the method used in the pre-, intra- and postoperative stages provided satisfactory results, also in relation to the postoperative mortality rate which relatively low compared to other published reports.