How Do Ring Size and π-Donating Thiolate Ligands Affect Redox-Active, α-Imino-N-heterocycle Ligand Activation?

Considerable effort has been devoted to the development of first-row transition-metal catalysts containing redox-active imino-pyridine ligands that are capable of storing multiple reducing equivalents. This property allows abundant and inexpensive first-row transition metals, which favor sequential one-electron redox processes, to function as competent catalysts in the concerted two-electron reduction of substrates. Herein we report the syntheses and characterization of a series of iron complexes that contain both π-donating thiolate and π-accepting (α-imino)-N-heterocycle redox-active ligands, with progressively larger N-heterocycle rings (imidazole, pyridine, and quinoline).

Phase III study of radiation therapy with or without cis-platinum in patients with unresectable squamous or undifferentiated carcinoma of the head and neck: an intergroup trial of the Eastern Cooperative Oncology Group (E2382).

Purpose: The Head and Neck Intergroup conducted a Phase III randomized trial to determine whether the addition weekly cisplatin to daily radiation therapy (RT) would improve survival in patients with unresectable squamous cell head-and-neck carcinoma.

Methods And Materials: Eligible patients were randomized to RT (70 Gy at 1.8-2 Gy/day) or to the identical RT with weekly cisplatin dosed at 20 mg/m(2).

Antibiotic prophylaxis in high-risk head and neck surgery: one-day vs. five-day therapy.

Patients who undergo major contaminated surgery of the head and neck benefit from perioperative antibiotic prophylaxis. This study was developed to determine if 5 days of antibiotic administration would be more effective than 1 day. A multi-institutional prospective randomized double-blind study was designed.

The role of endoscopy in evaluating patients with head and neck cancer. A multi-institutional prospective study.

In a prospective multi-institutional study of 384 patients undergoing endoscopy, an 8.9% incidence of second primary neoplasms was discovered simultaneously in the lung (3.3%), esophagus (1.

Assessment of mandibular invasion by carcinoma.

In this prospective study of 31 patients, the most sensitive assessment of malignant invasion of the mandible was by physical examination. Bone scanning and conventional roentgenographs are useful adjuncts in the staging evaluation of patients when clinical involvement is suspected and to determine the extent of disease in order to aid in treatment planning. However, they are frequently subject to false-positive interpretive errors, especially due to increased osteoblastic activity associated with dental disease and occasional tumor adjacent to the mandible.

Cisplatin potentiation of radiotherapy. Long-term follow-up.

Thirty-three patients with inoperable squamous cell carcinoma of the head and neck were treated with cisplatin, 15 mg/sq m, administered synchronously with high-dose radiation therapy. Twenty-nine patients (88%) responded to the regimen; of these, 20 had complete regression of all disease. Eight of the 20 had a relapse in less than one year of their treatment.

Nasal papillomas and squamous carcinoma.

There is a known association between carcinoma and nasal papillomatosis when benign nasal papillary lesions have been treated by radiotherapy or by chemotherapy. Invasive carcinoma was found in a patient with nasal papillomatosis that had not been treated previously. Ordinary inflammatory polyps involving the nasal and sinus cavities are extremely common and may mask papillomatosis.

Sphenoid wing meningioma occurring as a lateral orbital mass.

The differential diagnosis of a mass presenting in the lateral aspect of the orbit with bony erosion and involving the skin includes many malignancies, predominantly sarcomas. A total evaluation of the mass to include histopathologic characteristics and the true extent of the disease is critical to proper management of the patient. A 68-year-old man was referred for therapy with a diagnosis of fibrosarcoma.

The current status of mandibular reconstruction using autogenous frozen mandibular grafts.

A review of recent developments in experimental canine surgery using autogenous frozen grafts for mandibular reconstruction has elicited enthusiasm for their human application in cancer surgery. They do reossify, even under adverse conditions of perioperative irradiation, to regenerate a mandibular graft in the dog. Our experience with six patients who underwent immediate autogenous mandibular graft reconstruction is dismal.

Functional evaluation of the spinal accessory nerve after neck dissection.

The pain and dysfunction associated with a loss of innervation by the spinal accessory nerve has motivated surgeons to modify the classic radical neck dissection. A prospective study of 109 patients who underwent either a radical neck dissection or a modification of it with preservation of the spinal accessory nerve revealed that those patients in whom the nerve, muscle, and vein were preserved had less dysfunction (30 percent) than those with nerve preservation only (50 percent) or classic radical neck dissection (60 percent). In addition, even when the functional disability was the same, there was less associated pain with nerve-sparing procedures.

Cisplatin sensitization to radiotherapy of squamous cell carcinomas of the head and neck.

A combined modality of treatment utilizing cisplatin as a radiosensitizing agent concomitantly with full-course radical irradiation has been studied in 14 patients. Cisplatin at a dose of 15 mg/M2 body surface area was given intravenously on days 1 through 5 and 21 through 25 of the radiation therapy course. Among the 14 patients so treated, 11 patients had evidence of complete clinical regression of their tumors.

Bronchoscopy in the staging and evaluation of head and neck carcinoma.

There is no consensus of opinion regarding the use of routine bronchoscopy, either rigid or flexible, to evaluate patients with primary squamous cell carcinomas of the upper aerodigestive tract for the possibility of second synchronous primary cancers. Whereas there is certainty of the effectiveness of this endoscopy in patients with questionable lesions or masses on chest radiographs, the value of this procedure in the face of a normal, unequivocal chest radiograph remains questionable. Six patients with primary carcinomas in the upper head and neck region and normal chest radiographs were among 98 patients evaluated within the past 6 months by triple endoscopy.

Treatment of cervical lymph nodes in carcinoma of the tongue.

Treatment of the regional lymph nodes forms an integral part of the management of any patient with carcinoma of the tongue. It is the most important determinant of survival. Although survival correlates with the size of the primary tumor, it may also be explained by the higher incidence of metastatic nodes in larger lesions.

Small cell epidermoid carcinoma of salivary glands. 'Pseudo'-oat cell carcinoma.

Two patients had small cell carcinomas of the salivary glands, with pathological features indicating squamous differentiation, heretofore not described. One is free of disease at seven years, and the second is alive, with regional metastases at four years. Sections from one tumor were studied by electron microscopy and revealed tonofilaments and desmosomes.

Use of 1,2:5,6-dianhydrogalactitol in studies on cell kinetics-directed chemotherapy schedules in human tumors in vivo.

Recently, it has been shown that 1,2:5,6-dianhydrogalactitol (DAG) can cause reversible alterations in cell cycle kinetics. Following treatment of CHO cells in vitro and Ehrlich ascites tumor cells in vivo, significant increases in the fraction of cells in S phase were observed to occur, and this was followed by an increase in the fractions of cells in G2 and mitosis. Treatments with S or G2-M phase-specific drugs at the peak enrichment times after DAG was given resulted in greater cell kills than when given by any other schedule.

Carcinoma of the anterior tongue.

We have reviewed 126 patients with squamous cell carcinoma of the anterior tongue. Our experience suggests that carcinoma of the anterior tongue is a highly aggressive disease. It is no less aggressive and dangerous than carcinoma of the posterior tongue.

Massive congenital arteriovenous malformation of the pterygomaxillary space.

A case is presented of a massive congenital, extracranial arteriovenous malformation (AVM). The origins and hemodynamic considerations that led to prior treatment failure are discussed. A sudden accelerated growth in the AVM, caused by an alteration in the hemodynamics of the feeding and draining vessels, mandated further surgical management.

Immediate mandibular reconstruction: human experience with autogenous frozen mandibular grafts.

Autogenous mandibular grafts that have been cryosurgically devitalized and reimplanted have been studied in the canine. Initial investigations have lent impetus to further application in human cancer surgery. Six patients underwent immediate autogenous mandibular graft reconstruction.

Cervical nodal metastases of unknown origin.

A study of 48 patients with metastatic carcinoma in the neck from an unknown primary site has revealed several facts. Among patients with squamous cell carcinoma, the three-year survival rate was 40%. Whether treated with surgery (radical neck dissection) or with radical irradiation alone, the response of these tumors was similar in smaller N1 nodes; when treated with a combined therapeutic approach, they responded well in larger (N2 and N3) cervical nodes.

Dermal graft for protection of the pharyngeal suture line in cancer surgery of the head and neck.

We studied the effect of free buried dermal grafts to primary pharyngeal closures among 24 nonirradiated patients undergoing radical head and neck surgery to determine if this technique would reduce the incidence of postoperative pharyngocutaneous fistula. For a control group we selected 23 patients who had undergone similar operations as the patients in the study group, but who did not have dermis used for pharyngeal protection. Our results indicate that dermal grafts do not alter the incidence of fistulization following cancer surgery of the head and neck.

Neoglottic reconstruction following total laryngectomy. A reappraisal.

The purpose of this paper is to analyze the problems and complications which have resulted from neoglottic reconstruction at the University of Texas Medical Branch in Galveston. It has been performed as a primary procedure at the time of laryngectomy of 50 patients. Over 40% of these patients have required a second operative procedure to control major complications of their neoglottis.

Neoglottic reconstruction following total laryngectomy. The galveston experience.

A technique of primary neoglottic reconstruction for surgical restoration of voice following total laryngectomy is described in detail. This technique has been performed on 30 patients at the University of Texas Medical Branmch, and our results are reported. Twenty (67%) of these patients are speaking with their neoglottises after one year.

Replacement of tumor-involved mandible by cryosurgically devitalized autograft: human experience.

In management of a malignant floor-of-mouth tumor invading the mandible, the mandible is the main focus of reconstruction and the most likely site of rehabilitative failure. Creation of a functional and cosmetically appealing replacement is a major therapeutic goal. In canines, neoosteogenesis does occur in mandibular autografts exposed to two consecutive freeze-thaw cycles prior to reimplantation.