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.

Sexuality after laparoscopic Davydov in patients affected by congenital complete vaginal agenesis associated with uterine agenesis or hypoplasia.

BACKGROUND: Several surgical techniques have been described for the treatment of patients with vaginal agenesis. The simplest intervention that gives good sexual results should be the surgical technique of choice. METHODS: We report anatomic and functional outcome in 28 women after vaginoplasty using laparoscopic Davydov operation. This surgery includes three steps: two laparoscopic and one perineal. The patient then has to use a mould or a vaginal dilatator for 1 month. The functional outcome was assessed by a brief and valid self-report questionnaire evaluating female sexual life (Female Sexual Function Index, FSFI). A control group was recruited to compare the results. RESULTS: Two intra-operative bladder and ureteric injuries were repaired without sequels. Two post-operative complications were observed: one abdominal migration of the mould, which was treated successfully with the laparoscope, and one vesico-vaginal fistula. No patient was lost to follow-up. The anatomical result was judged to be satisfactory (>6 cm) in 26 of the 28 patients: the mean vaginal length was 7.2 +/- 1.5 cm. Among the 28 operated women, 19 had a good or very good result. No statistical difference was found between our operated patients and French controls in all six domains of the FSFI. CONCLUSIONS: Laparoscopic Davydov may be considered a good option for the surgical treatment of women presenting vaginal agenesis. This technique offers advantages such as: short operating time and hospital stay, no particular instrumentation required and no external scars. Sexuality approaches so-called 'normal sexuality'.

Effect of radiotherapy on pelvic lymph node metastasis in cervical cancer stages IB2-IVA: a retrospective analysis of two comparative series.

Efficiency of radiotherapy in controlling lymph node metastasis is a controversial issue. A continuous series of 87 patients affected by cervical cancer stages IB2-IVA and treated using pelvic radiotherapy is presented. A retrospective comparison is made between two populations. In the two populations, a staging lymphadenectomy was carried out before the onset of the therapeutic program. In the first population (53 patients), the pelvic nodes only were dissected and in the second one (34 patients), the pelvic lymph nodes were left in place and the paraaortic nodes only were dissected. In both series, a completion surgery was performed after finalization of the radiotherapy. It was carried out at open abdomen in both series. It included a systematic pelvic dissection for the patients whose pelvic nodes had been intentionally left in place at the time of the initial staging lymphadenectomy. Both series were identical as far as classic risk factors were concerned (FIGO stage, maximal tumor diameter, lymphovascular space involvement). The radiotherapy administered to the pelvis was the same in both populations. The number of patients with pelvic lymph node metastasis was 21 (39.6%) in the first population versus 6 (17.6%) in the second one (P = 0.03). The percentage of positive lymph nodes among the retrieved lymph nodes was 18.94 in the first population versus 2.8 in the second one (P = 0.0001). Pelvic radiotherapy is likely to control most of the pelvic lymph node metastasis, but not all of them. Practical deductions and further developments are discussed.

[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).

[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.

[Laparoscopy in the management of uterine cancers]. / La coelioscopie dans la prise en charge des cancers de l'utérus.

There are two places for laparoscopic surgery in the management of uterine cancer. For the patients who have to be submitted to primary surgery the laparoscope enables us to select the ones who can be operated without laparotomy (no lymph nodes involvement after laparoscopic lymphadenectomy) and to make easier the "minimal access surgery" (laparoscopically assisted vaginal hysterectomy and radical hysterectomy). For the patients who have to be submitted to radiotherapy (and concomitant chemotherapy), the laparoscope enables us to select the ones for whom an extended field radiotherapy is useless (no aortic lymph nodes involved after laparoscopic lymphadenectomy) and to perform an ovarian transposition which protects the ovarian function of young patients.

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.

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.

Neoadjuvant chemotherapy for unresectable ovarian carcinoma: a French multicenter study.

BACKGROUND: Initial debulking surgery followed by chemotherapy is the current treatment for International Federation of Gynecology and Obstetrics Stage IIIC/IV ovarian carcinoma but has a limited efficacy when optimal cytoreduction is not achieved at the end of the surgical procedure. An alternative treatment for these patients could be neoadjuvant chemotherapy. The purpose of this retrospective study was to report the results of neoadjuvant chemotherapy in operable patients (no medical contraindication to surgery) presenting with primary unresectable tumors. METHODS: Between January 1996 and March 1999, operable patients presenting with Stage IIIC or IV ovarian carcinoma underwent, in six French gynecologic oncology departments, surgical staging to evaluate tumor resectability. When the tumor was deemed unresectable by standard surgery, the patient received three to six cycles of platinum-based neoadjuvant chemotherapy according to the response and the center's usual protocol. Patients were surgically explored after completion of neoadjuvant chemotherapy when the tumor did not progress during treatment. Debulking was performed during this secondary surgery when a response to chemotherapy was observed. RESULTS: Fifty-four patients were treated by neoadjuvant chemotherapy. The first surgical staging procedure was laparoscopy in 33 patients (61%) and laparotomy in 21 patients (39%). The median number of neoadjuvant chemotherapy cycles was 4 (range, 0-6). Forty-three patients (80%) responded to neoadjuvant chemotherapy and then tumors were debulked. Optimal cytoreduction was obtained in 39 patients (91% of the patients who underwent debulking) and with standard surgery in 32 patients (82%). For patients whose tumors were optimally debulked, blood transfusions were administered to 17 patients (43%), median intensive care unit stay was 0 days (range, 0-7 days), and median postoperative hospital stay was 10 days (range, 4-62 days). Median overall survival for the total series was 22 months. Survival was better for patients debulked after neoadjuvant chemotherapy compared with patients with nondebulked tumors (P < 0.001). CONCLUSIONS: Neoadjuvant chemotherapy for primary unresectable ovarian carcinoma leads to the selection of a subset of patients sensitive to chemotherapy in whom optimal cytoreduction can be achieved after chemotherapy by standard surgery in a high proportion of cases. Conversely, aggressive surgery can be avoided in patients with initial chemoresistance, in whom the prognosis is known to be poor regardless of treatment.

Extraperitoneal laparoscopic para-aortic lymph node dissection for early stage nonseminomatous germ cell tumors of the testis with introduction of a nerve sparing technique: description and results.

PURPOSE: The extraperitoneal approach is well suited to urological surgery. Transperitoneal laparoscopic para-aortic lymph node dissection has been reported with good results for early stage nonseminomatous germ cell tumor of the testis. We report our current experience with laparoscopic para-aortic lymph node dissection using a new extraperitoneal approach. MATERIALS AND METHODS: The technique consists of an internal iliac extraperitoneal approach and complete unilateral modified laparoscopic para-aortic lymph node dissection. We assessed 25 patients with clinical stage I (20) or IIA (5) testicular nonseminomatous germ cell tumor who underwent this technique, including left and right lymphadenectomy in 13 and 12, respectively. In addition, nerve sparing dissection was performed in the last 12 cases. RESULTS: An average of 9.8 (range 3 to 19) and 17. 7 (range 5 to 29) lymph nodes were dissected on the right and left sides, respectively. No intraoperative or postoperative complications developed that required laparotomy. Average operative time was 3 hours 50 minutes (range 3 to 5 hours). Average hospital stay was 1.2 days (range 1 to 3). Results were positive in 10 patients who were given platinum based chemotherapy. At close followup of 15 months no late adverse effects or recurrence was observed. CONCLUSIONS: Although a larger experience and longer followup are required, extraperitoneal laparoscopy is a safe, effective and well suited method of diagnostic para-aortic lymph node dissection for early stage testicular nonseminomatous germ cell tumor. The specific advantages of this approach are no blind trocar insertion or bowel contact and ability to perform nerve sparing dissection. Moreover, it is cost-effective since only 3 trocars are necessary and recovery is rapid.

[Role of ultrasound guided puncture in the management of ovarian cysts]. / Place de la ponction écho-guidée dans la prise en charge des kystes ovariens.

Ultrasound guided aspiration of ovarian cysts should be performed in well defined indications and under precise and strict modalities. Preoperative evaluation should include vaginal sonography and serum levels of CA125 and CA 19/9. Ultrasound guided aspiration is allowed only in cases of sonographically benign cyst: unilateral unilocular homogenous anechogenic cyst less than 7 cm, and serum levels of CA125 and CA 19/9 less than 35 Ul/ml. The technique of ultrasound guided aspiration is similar to the one used for oocytes recovery in in vitro fertilization treatments. It is mandatory to perform a macroscopic, cytologic and biologic (with concentrations of estradiol, CA125 and CA 19/9) evaluation of cyst fluid. Patients should be told that in case of abnormalities of cyst fluid, a laparoscopy has to be performed immediately or as soon as possible, and that there is a risk of recurrence of the ovarian lesion.