Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations.

The complexes of diacetyl with water have been studied experimentally by Fourier transform infrared (FTIR) spectroscopy coupled to solid neon matrix and supersonic jet, and anharmonic ab initio calculations. The vibrational analysis of neon matrix spectra over the 100-7500 cm-1 infrared range confirms the existence of two nearly isoenergetic one-to-one (1/1) diacetyl-water S1 and S2 isomers already evidenced in a previous argon matrix study. A third form (S3) predicted slightly less stable ( J. Mol. Mod. 2015 , 21 , 214 ) is not observed. The correct agreement obtained between neon matrix and anharmonic calculated vibrational frequencies is exploited in several cases to derive band assignments for the vibrational modes of a specific isomer. Thereafter, theoretical xij anharmonic coupling constants are used for the attribution of combination bands and overtones relative to the 1/1 dimer. Finally, the most stable isomer of the one-to-two (1/2) diacetyl-water complex is identified in the OH stretching region of water on the grounds of comparison of experimental and calculated vibrational shifts between water dimer and the three most stable 1/2 isomers.

Topological insights into the 1/1 diacetyl/water complex gained using a new methodological approach.

The 1/1 diacetyl/water complex is of atmospheric relevance. Previous experimental and theoretical studies have focused on two isomeric forms, and geometry optimizations were carried out on them. Herein, we propose a six-step methodological approach based on topological properties to search for and characterize all of the isomeric forms of the 1/1 noncovalent diacetyl/water complex: (1) a molecular electrostatic potential (MESP) study to get an overview of the V min and V max regions on the molecular surfaces of the separate molecules (diacetyl and water); (2) a topological (QTAIM and ELF) study allowing thorough characterization of the electron densities (QTAIM) and irreducible ELF basins of the separate molecules; (3) full optimization of the predicted structures based on the interaction between complementary reaction sites; (4) energetic characterization based on a symmetry-adapted perturbation theory (SAPT) analysis; (5) topological characterization of the optimized complexes; (6) analysis of the complexes in terms of orbital overlaps (natural bond orbitals, NBO analysis). Using this approach, in addition to achieving the topological characterization of the two isomeric forms already reported, a third possible isomer was identified and characterized. Graphical Abstract Topological tools to study monohydrated complexes.

Intraoperative radiation therapy in recurrent carcinoma of the uterine cervix: report of the French intraoperative group on 70 patients.

PURPOSE: To evaluate the feasibility and oncologic results of intraoperative radiation therapy (IORT) for recurrent uterine cervical carcinoma in a cohort of patients treated in seven French institutions. METHODS AND MATERIALS: From 1985 to 1993, 70 patients with pelvic recurrences underwent IORT with/ without external radiation therapy (ERT) and chemotherapy (CT). Treatment modalities for recurrence were IORT alone (40 out of 70), IORT + ERT (30 out of 70), additional chemotherapy (20 out of 70). Gross complete resection (CR) was performed in 30 out of 70 cases, partial resection (PR) in 37 out of 70, and unspecified surgery in 3 out of 70. Sixty-five patients had electron beam IORT and 5, 100 KV photon IORT. Mean IORT cone size, electron beam energy, and dose (calculated at the 90% isodose line) were, respectively, 75 mm (40 to 90), 12 MeV (6 to 20), and 18 Gy (10 to 25) after CR and 80 mm (45 to 100), 15 MeV (7 to 24), and 19 Gy (10 to 30) after PR. RESULTS: Mean follow-up after IORT was 15 months (2 to 69). One, 2- and 3-year overall survival rates were 47, 17, and 8%, respectively; median survival was 11 months and local control, 21%. Median survival and local control rates increased after CR (13 months, 27%) vs. PR (10 months, 17%) and when initial treatment consisted of surgery (S) alone (15 months, 25%) vs. radiation therapy (RT +/- S) (10 months, 16%). However, these differences were not statistically significant. No death-related toxicity was observed. Grade 2 or 3 toxicity was observed in 19 out of 70 patients (27%), including 9 not directly IORT-related complications (13%) (three digestive tract fistulas, one rectal stricture, three urinary fistulas, two infections) and 10 directly IORT-related complications (14%) (five neuropathies, four ureteral obstructions, and one rectal stricture). CONCLUSION: This retrospective study demonstrates the feasibility of IORT. The usefulness of IORT still needs to be evaluated in primary treatment of advanced stages of cervical carcinoma.

Morphometric differentiation between responsive tumor cells and mesothelial hyperplasia in second-look operations for ovarian cancer.

We developed a procedure based on computerized image analysis to establish objective criteria for the differential diagnosis between mesothelial hyperplasia and cancer in peritoneal tissue samples obtained at second-look operations for ovarian cancer. The tumor tissue after chemotherapy was classified as "nonresponsive" if it was found by histologic criteria to be roughly similar to the tumor before chemotherapy and as "responsive" if it was found to be different (small clusters of bland-looking cells with no mitotic activity). Eighty-five samples of tissue had been classified previously by a pathologist into one of the four following groups: ovarian tumor prior to chemotherapy, "responsive" tumor, "nonresponsive" tumor, or mesothelial hyperplasia. Cell profiles of the tissue samples were studied by computerized image analysis using 21 morphometric descriptors derived from the manual tracings of tumor nuclei, including nuclear perimeter, nuclear area, maximal chord, circularity factor, and standard deviations of these descriptors. Size distribution curves of nuclear areas and maximal chords were included in the analysis. A multivariate discriminant analysis confirmed the separation into the four diagnostic groups, accomplished with consideration of the physical descriptors alone, except for some overlapping between groups 1 and 3. The separation between carcinoma and mesothelial hyperplasia was clear in all cases.

Laparoscopic techniques for gynecologic cancer: description and indications.

This article reviews the role of laparoscopic surgery in gynecologic oncology. The first part describes laparoscopic staging techniques. The second part describes surgical tumor-removal techniques. The third part discusses the indications for laparoscopic surgery in different types of gynecologic cancer.

[Treatment of cancer of the uterine cervix by surgery alone]. / Le traitement du cancer du col utérin par la seule chirurgie.

The authors report a series of 434 patients with invasive cancer of the uterine cervix treated with primary surgery. The results are equivalent to those reported by others who treated cervix cancer with radiotherapy. Post-operative radiotherapy did not improve the results except in the most advanced forms (pT2b, pN1 or 2) when it increases the disease-free interval without altering the survival probability at 5 years. For the clinical stages I, IIA and IIB proximal (infiltration of the parametrium limited to the proximal part) surgery is the elective treatment. In stage IIB distal and for "operable" Stages III and IV, a combination of chemotherapy-surgery and radiotherapy is suggested.

Laparoscopic surgery in gynecologic oncology.

Laparoscopy found its first application in the field of gynecology. Today, laparoscopy benefits the general gynecologist because of its minimally invasive nature. Benign procedures, such as oophorectomies and hysterectomies, have become practically outpatient procedures. The learning curve for laparoscopy in gynecologic cancer operations is obviously steeper, more time consuming, and training-dependent. With increased operative time, cost, and the questions of safety in malignant conditions, laparoscopy has quite a burden of proof before it becomes widely accepted. This article reviews the current applications of laparoscopy in gynecologic oncology with available data and offers future directions best suited for laparoscopy in this subspecialty.

Influence of vitamin E administration on platelet functions in hormonal contraceptive users.

Platelet functions (aggregation, clotting activity), platelet lipid biosynthesis, sterol composition and phospholipid fatty acids were studied in relation to plasma lipids and fatty acids as well as dietary habits at day 5 and 21 of the menstrual cycle in 30 women having used hormonal contraceptive for several years. The women were studied again on day 21 of the second cycle after they had taken for two months 200 mg vitamin E per day in addition to the contraceptive. At day 21 (after 3 weeks of hormonal contraceptive) as compared to day 5, there was a significant increase in the clotting activity of platelets and the response to ADP-induced aggregation concomitant with a decrease in plasma vitamin E. After vitamin E administration, platelet activity at day 21 was markedly decreased, being similar to the activity at day 5, with a significant increase in the level of vitamin E in plasma and platelets. The high response of platelets to aggregation in women using contraceptives does not seem to be associated with the intake of saturated fat but rather with that of 18:2. The aggregation to thrombin was mostly related to lanosterol biosynthesis and the aggregation to ADP to platelet cholesterol, but not to plasma lipids or apoproteins. The present pilot study suggests that the platelet hyperactivity of long-term hormonal contraceptive users might be dependent upon a low level of platelet alpha-tocopherol which can be rapidly overcome by giving a supplement of vitamin E.

PIP: Platelet functions (aggregation, clotting activity), platelet lipid biosynthesis, sterol composition and phospholipid fatty acids were studied in relation to plasma lipids and fatty acids as well as dietary habits at day 5 and 21 of the menstrual cycle in 30 women who used oral contraceptives (OCs) for several years. The women were studied again on day 21 of the 2nd cycle after they had taken 200 mg vitamin E/day for 2 months in addition to the OCs. At day 21 (after 3 weeks of OC use) there was a significant increase in the clotting activity of platelets and the response to ADP-induced aggregation concomitant with a decrease in plasma vitamin E. After vitamin E administration, platelet activity at day 21 was markedly decreased, being similar to the activity at day 5, along with a significant increase in the level of vitamin E in plasma and platelets. The high response of platelets to aggregation in women taking OCs does not seem to be associated with the intake of saturated fat but rather with that of 18:2. The aggregation to thrombin was mostly related to lanosterol biosynthesis and the aggregation to ADP to platelet cholesterol, but not to plasma lipids or apoproteins. The present pilot study suggests that the platelet hyperactivity of longterm OC users might be dependent on a low level of platelet alpha-tocopherol which can be rapidly overcome by administering a vitamin E supplement.

Obstetrical prognosis of the septate uterus: a plea for treatment of the septum.

OBJECTIVE: To evaluate the obstetrical and perinatal implications of the septate uterus and assess the improvements of the prognosis after treatment of the septum. INVESTIGATION: This retrospective investigation was carried out in a single centre on 78 patients with septate uterus who had previously been correctly classified. A total of 203 pregnancies were observed. All complications occurring during the first, second and third trimesters and the neonatal outcome were logged. Furthermore, 25 patients in this sample underwent surgery which enabled reassessment of the obstetric and neonatal outcome. RESULTS: Prior to surgery, during the 203 pregnancies, the fetal loss rate during the first two trimesters was 47%, prematurity 17% and 89 children were alive, i.e. an overall perinatal mortality rate of 16.8% when pregnancy exceeded 24 weeks. After surgical treatment of the septum, the proportion of pregnancies proceeding subsequent to 24 weeks and infant survival changed, respectively, from 13.3% to 90% and from 4.4% to 87.5%. CONCLUSION: The obstetric and neonatal prognosis of septate uteruses is extremely unfavourable. This is radically transformed by treating the septum.

Operative injuries during vaginal hysterectomy.

OBJECTIVE: To evaluate incidence, characteristics and consequences of urinary and intestinal tract injuries during vaginal hysterectomy for benign conditions. STUDY DESIGN: From January 1970 to December 1996, 3076 vaginal hysterectomies with or without additional procedures, were performed for benign conditions in our department. We retrospectively analyzed operative injury cases. RESULTS: Incidence of urinary and intestinal tract injuries were 1.7 and 0.5%, respectively. Concerning urinary tract injuries, we observed only one ureteral lesion, all others being bladder lacerations (54 cases). The bladder lacerations occured during the hysterectomy step of the surgery in 61% of cases and during the additional procedures in 39%. All bladder injuries were recognized and treated during the primary operation. We observed four cases of vesico-vaginal fistula as a consequence of these injuries; all fistulas occured after bladder laceration during the hysterectomy step of the surgical procedure. Intestinal tract injuries (16 cases) were rectal lacerations occuring during the hysterectomy step of the surgery (31% of cases) and during the additional procedures (69%). All rectal injuries were recognized and repaired during the primary operation and all healed without sequellae. CONCLUSION: Operative injuries during vaginal hysterectomy are relatively rare. They are easily recognized and treated during the primary operation without important sequellae.

The use of micronized progesterone in the treatment of menace of preterm delivery.

The results of a study concerning the treatment of acute menace of preterm labor are given: beta-mimetics were administered intravenously in all cases (44) and micronized progesterone or placebo was administered orally after classical double-blind randomization (22 cases in each group). The mean index of pregnancy prolongation was the same in both groups. However the mean duration of the intravenous perfusion and the mean quantity of beta-mimetics administered intravenously were significantly reduced in the progesterone group (P less than 0.01). The mean duration of hospital stay was also significantly reduced (P less than 0.05). Cost and risks are finally significantly lessened.

[Primary surgery in the treatment of stage I and "slight" stage II carcinoma of the cervix (author's transl)]. / La chirurgie première dans le traitement du cancer cervico utérin au stade I et au stade II "faible".

A group of 140 patients with stage I and "slight" stage II invasive carcinoma of the cervix undergoing surgery without prior irradiation between October 1st and October 31st 1978 is presented. The 5 year survival rate, taking into account the actual characteristics of the series, corresponded to the average usually found. Primary surgery makes it possible to limit indications for irradiation to cases where there exists either true infiltration of pelvic tissue or lymph node metastases which can be assessed only by examination of an operative specimen. It is thus also possible to avoid "radiotherapy menopause" in a large number of women (in 68 of the 81 patients aged less than 50 years in the present series).

[Study with serial sectioning of 312 preclinical cancers of the uterine cervix. Indications for selective treatment (author's transl)]. / Etudes par coupes sériées de 312 cancers pré-cliniques du col utérin. Déductions thérapeutiques.

The authors have studied by step serial sectioning 312 cervix the most obtained by cold knife conization. They have studied too, the frequency of inadequate resection (i.e. non in sano conization) and clinically occult invasion according to the age of patients. Conization is adequate for the treatment of 70 per cent of women less than 30 years of age. But after 50 it is sufficient in only 22 per cent of the patients. Conization must be performed in most cases of grade III to V cervical smear (according to Papanicolaou's classification). The cervical cone must be studied by serial sectioning (every 500 microns). According to the result of this study the treatment must be selected : conization for in situ carcinoma resected in sano, simple hysterectomy for in situ carcinoma not resected in situ and Wertheim type operation for invasive carcinoma.

[Sensitivity and specificity of two methods used to identify incident breast cancer in specialized units using claims databases]. / Sensibilité et spécificité de deux méthodes d'identification des cancers du sein incidents dans les services spécialisés à partir des données médico-administratives.

BACKGROUND: Hospital claims databases from acute care units are available nationwide and contain most patients at the beginning of their cancer. The goal is to define the ability of these databases to provide a number of incident breast cancer cases using identification methods. Two identification methods were assessed in three specialized sections of a teaching hospital. METHODS: The first method identified women who had at least one stay with a principal diagnosis of breast cancer. The second, which is more restrictive, identified women who had at least one stay with a principal diagnosis of breast cancer and a breast cancer-specific surgical treatment code. Both methods were applied to 4588 women 20 Years of age or older hospitalized in three specialized sections of the Hospices Civils de Lyon in 2000. To categorize these women in two groups, incident breast cancer cases or non-incident breast cancer cases, 150 women were randomized in each of two groups, one for incident breast cancer cases and one for non-incident breast cancer cases. Their medical records were used as references. RESULTS: Sensitivity, specificity and their credibility intervals were respectively 99.4% (84-99.9) and 91.7% (90.3-93.3) for the first method and 93.8% (76.2-98.7) and 97.3% (96.1-98) for the second. Among women wrongly identified with an incident breast cancer in 2000, 75.4% (43/57) had a breast cancer that was not incident that Year with the first method, compared to 96% (24/25) with the second. Among these women wrongly identified with an incident breast cancer, coding errors of the principal diagnosis were found for 24.6% (14/57) of patients with the first method and for 4% (1/25) with the second. Their correction led to 99.2% (86.5-99.9) sensitivity and 92.9% (91.4-94.6) specificity for the first method and to 94.2% (76.5-98.7) sensitivity and 97.3% (96.2-98.1) specificity for the second. CONCLUSIONS: The second method using cancer-specific surgical codes appeared more specific with a slight loss in sensitivity. The use of identification methods to assess the number of incident cancer cases still have to be defined.

[Fertility preservation in early cervical cancer]. / La préservation de la fertilité dans les cancers du col utérin de stade précoce.

OBJECTIVE: Evaluation of surgical techniques leading to fertility preservation in patients with early cervical cancer. PATIENTS AND METHODS: Carcinological and obstetrical follow-up of 95 patients treated with radical trachelectomy between 1987 and 2002 for a cervical cancer stage less than Ib2. RESULTS: Four recurrences were observed; all of these were in case of tumor more than 2 cm in diameter (P = 0.002), and three of the four recurrences were in case of lymph-vascular space involvement (P = 0.07). Among the 42 patients willing and able to procreate, 33 were pregnant. Fifty-six pregnancies were registered. The rate of late miscarriage was 19% and 34 living newborns were obtained. CONCLUSION: In case of early cervical cancer, radical trachelectomy preserves fertility, leading to a good rate of living newborns without impairing the chances of survival.

[Insertion of a sub-urethral sling through the obturating membrane for treatment of female urinary incontinence]. / Pose d'un ruban sous urétral oblique par voie obturatrice dans le traitement de l'incontinence urinaire féminine.

OBJECTIVE: The use of a TVT device has been for a few years the operation most often performed to treat female urinary incontinence. One of the most frequent complications of this surgery is bladder perforation. MATERIAL AND METHODS: To prevent this complication we use the way initially suggested by Delorme, in which the two ends of the sling were passed through the obturating membrane and the muscles which cover it, by circumventing the ischiopubic bone with Emmet needle introduced from outside to inside. RESULTS: No bladder perforation was noted among the first 71 operated patients. For the first 68 patients re-examined 6 to 12 weeks after the surgery, two patients had improved and 64 were totally cured. CONCLUSION: The effectiveness of this method is the same as that of the traditional method.

[Laparoscopic Davydov or laparoscopic transposition of the peritoneal colpopoeisis described by Davydov for the treatment of congenital vaginal agenesis: the technique and its evolution]. / Le Davydov coelioscopique ou transposition coelioscopique du colpopoiesis péritonéal pelvien décrit par Davydov pour le traitement des agénésies congénitales du vagin: la technique et son évolution.

INTRODUCTION: The laparoscopic Davydov is described. The data concerning the surgery and the postoperative course are reported at the same time as the data concerning the anatomical and sexological results. PATIENTS AND METHODS: The surgery includes three steps: (i) cleavage under laparoscopic guidance, (ii) peritoneovestibular stitch by perineal approach, (iii) making the vaginal vault with the laparoscope. The cleavage can be performed in front of the fascia interposed between the bladder and the rectum or behind it. A nymphoplasty can be added to the colpopoeisis. RESULTS: Between February 1996 and March 2003 we operated on 28 patients affected by congenital vaginal agenesis using the laparoscopic Davydov technique. Two peroperative complications occurred (urinary tract injuries during the first step: laparoscopic management) and two postoperative complications (intraperitoneal migration of the mould and vesicovaginal fistula managed successfully with the laparoscope for the first one and trough laparotomy for the second one). Four re-operations (incision and dilation) were necessary. The length of the neovagina was, at the last assessment, 7.2 +/- 1.3 cm. The Female Sexual Function Index was 26.5 +/- 5.6 vs. 27.9 +/- 4.5 in a control cohort. In the patients whose cleavage was performed behind the fascia (13 cases vs. 15) no complication occurred, no re-operation was necessary, the length of the neovagina was 7.0 +/- 0.7 cm and the FSFI was 26.3 +/- 5.9. DISCUSSION AND CONCLUSION: The laparoscopic Davydov is, if the dorsal approach is used for the cleavage, an easy to make operation (operating time: 90 +/- 29 minutes) with a short hospital stay. The postoperative care is simple (vaginal mould useless). Heterosexual activity with penile penetration can start early (6 to 8 weeks). The level of satisfaction is high. Laparoscopic Davydov procedure may be considered a good alternative to the more complex ones (as Vecchietti's technique) or to the more dangerous ones (sigmoid colpoplasty).

[Laparoscopic surgery in gynecologic oncology]. / La chirurgie laparoscopique en gynécologie oncologique.

Panoramic retroperitoneal pelviscopy, introduced in 1987 was the first of the laparaoscopic operations used in the field of gyneceologic oncology. It was divised in order to enable the assessment of the pelvic lymph nodes prior to decision making in the management of patients with early cervical cancer. Starting from 1992, laparaoscopic surgery to all fields of gynecologic oncology and all the operations of the classical repertoire were transcribed in the new repertoire. This evolution is not without danger. Direct manipulation of an organ harboring a malignant tumor increases the chances of diffusion of malignant cells. Working with micro-instruments under CO(2) insufflation is likely to favor chances of dissemination. The true place of laparoscopic surgery is, as it has assuredly been since the beginning of its use, in the assessment of tumor surroundings and not in direct manipulation of the organ harboring the tumor. In the cases where imaging clearly shows regional and/or distal spread, it would be better to avoid laparoscopic dissection and retrieval. The most difficult problem in laparaoscopic onco-surgery is not the surgery itself, but in determining in which cases is can be used and in which it cannot.

[Cervical coagulation (author's transl)]. / La coagulation du col.

Coagulation of the cervix is one of the most frequently carried out gynaecological procedures. All the same, protagonists and antagonists produce numerous arguments about the indications for the operation, the best techniques to adopt and whether it does have any prophylactic action against cancer. The author, in this article, which reviews the arguments and counter-arguments, summarises the opinion of several specialists about this matter. The advice given seems to be very divided as far as the indications are concerned, the author himself reserving coagulation especially for those cervices from which pathological discharges emanate, after he has controlled the state by smears and colposcopy, and has considered atypical epithelia as a contra-indication to coagulation. The variety of techniques in use prove that the problem has not been resolved. To bipolar diathermy coagulation has followed cryosurgery and coagulation at 90 degrees C. Finally, the prophylactic role against cancer is discussed. Whatever the attitude taken, coagulation of the cervix does not mean that follow-up may be dispensed with.

[Spinous fixation (vaginae fixatio sacrospinalis) in the treatment of vaginal prolapse after hysterectomy]. / La spino-fixation (vaginae fixatio sacro spinalis) dans le traitement des prolapsus du dôme vaginal après hystérectomie.

The authors describe an operation for treating true prolapse of the vagina which can follow total hysterectomy. The vault is fixed to the little sacro-coccygeal ligament. They report 133 case histories. The results are very good indeed in 60% of cases. True failures are rare: 2 out of 100 cases in Richter's series and 3 out of 12 cases in Dargent's series.