Probing equilibrium of molecular and deprotonated water on TiO2(110).

Understanding adsorbed water and its dissociation to surface hydroxyls on oxide surfaces is key to unraveling many physical and chemical processes, yet the barrier for its deprotonation has never been measured. In this study, we present direct evidence for water dissociation equilibrium on rutile-TiO2(110) by combining supersonic molecular beam, scanning tunneling microscopy (STM), and ab initio molecular dynamics. We measure the deprotonation/protonation barriers of 0.36 eV and find that molecularly bound water is preferred over the surface-bound hydroxyls by only 0.035 eV. We demonstrate that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The developed methodology for studying metastable reaction intermediates prepared with a high-energy molecular beam in the STM can be readily extended to other systems to clarify a wide range of important bond activation processes.

Anticorrelation between surface and subsurface point defects and the impact on the redox chemistry of TiO2(110).

By using a combination of scanning tunneling microscopy (STM), density functional theory (DFT), and secondary-ion mass spectroscopy (SIMS), we explored the interplay and relative impact of surface versus subsurface defects on the surface chemistry of rutile TiO2 . STM results show that surface O vacancies (VO ) are virtually absent in the vicinity of positively charged subsurface point defects. This observation is consistent with DFT calculations of the impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 was employed and was observed to be suppressed around them. DFT results attribute this to a perceived absence of intrinsic (Ti), and likely extrinsic interstitials in the nearest subsurface layer beneath inhibited areas. We also postulate that the entire nearest subsurface region could be devoid of any charged point defects, whereas prevalent surface defects (VO ) are largely responsible for mediation of the redox chemistry at the reduced TiO2 (110).

First-principles study of phenol hydrogenation on Pt and Ni catalysts in aqueous phase.

The effect of an aqueous phase on phenol hydrogenation over Pt and Ni catalysts was investigated using density functional theory-based ab initio molecular dynamics calculations. The adsorption of phenol and the addition of the first and second hydrogen adatoms to three, ring carbon positions (ortho, meta, and para with respect to the phenolic OH group) were explored in both vacuum and liquid water. The major change in the electronic structure of both Pt(111) and Ni(111) surfaces, between a gaseous and liquid phase environment, results from a repulsion between the electrons of the liquid water and the diffuse tail of electron density emanating from the metal surface. The redistribution of the metal's electrons toward the subsurface layer lowers the metal work function by about 1 eV. The lower work function gives the liquid-covered metal a higher chemical reduction strength and, in consequence, a lower oxidation strength, which, in turn lowers the phenol adsorption energy, despite the stabilizing influence of the solvation of the partly positively charged adsorbate. At both the solid/vapor and the solid/water interface, H adatom addition involves neutral H atom transfer hence the reaction barriers for adding H adatoms to phenol are lowered by only 10-20 kJ/mol, due to a small stabilizing at the transition state. More importantly, the liquid environment significantly influences the relative energetics of charged, surface-bound intermediates and of proton-transfer reactions like keto/enol isomerization. For phenol hydrogenation, solvation in water results in an energetic preference to form ketones as a result of tautomerization of surface-bound enol intermediates.

Site-specific imaging of elemental steps in dehydration of diols on TiO(2)(110).

Scanning tunneling microscopy is employed to follow elemental steps in conversion of ethylene glycol and 1,3-propylene glycol on partially reduced TiO2(110) as a function of temperature. Mechanistic details about the observed processes are corroborated by density functional theory calculations. The use of these two diol reactants allows us to compare and contrast the chemistries of two functionally similar molecules with different steric constraints, thereby allowing us to understand how molecular geometry may influence the observed chemical reactivity. We find that both glycols initially adsorb on Ti sites, where a dynamic equilibrium between molecularly bound and deprotonated species is observed. As the diols start to diffuse along the Ti rows above 230 K, they irreversibly dissociate upon encountering bridging oxygen vacancies. Surprisingly, two dissociation pathways, one via O-H and the other via C-O bond scission, are observed. Theoretical calculations suggest that the differences in the C-O/O-H bond breaking processes are the result of steric factors enforced upon the diols by the second Ti-bound OH group. Above ∼400 K, a new stable intermediate centered on the bridging oxygen (Ob) row is observed. Combined experimental and theoretical evidence shows that this intermediate is most likely a new dioxo species. Further annealing leads to sequential C-Ob bond cleavage and alkene desorption above ∼500 K. Simulations demonstrate that the sequential C-Ob bond breaking process follows a homolytic diradical pathway, with the first C-Ob bond breaking event accompanied with a nonadiabatic electron transfer within the TiO2(110) substrate.

The role of reducible oxide-metal cluster charge transfer in catalytic processes: new insights on the catalytic mechanism of CO oxidation on Au/TiO2 from ab initio molecular dynamics.

To probe metal particle/reducible oxide interactions density functional theory based ab initio molecular dynamics studies were performed on a prototypical metal cluster (Au20) supported on reducible oxides (rutile TiO2(110)) to implicitly account for finite temperature effects and the role of excess surface charge in the metal oxide. It is found that the charge state of the Au particle is negative in a reducing chemical environment whereas in the presence of oxidizing species coadsorbed to the oxide surface the cluster obtained a net positive charge. In the context of the well-known CO oxidation reaction, charge transfer facilitates the plasticization of Au20, which allows for a strong adsorbate induced surface reconstruction upon addition of CO leading to the formation of mobile Au-CO species on the surface. The charging/discharging of the cluster during the catalytic cycle of CO oxidation enhances and controls the amount of O2 adsorbed at oxide/cluster interface and strongly influences the energetics of all redox steps in catalytic conversions. A detailed comparison of the current findings with previous studies is presented, and generalities about the role of surface-adsorbate charge transfer for metal cluster/reducible oxide interactions are discussed.

Expression of matrix metalloproteinase-12 is correlated with extracapsular spread of tumor from nodes with metastasis in head and neck squamous cell carcinoma.

Matrix metalloproteinases (MMPs) play an important role in tumor invasiveness and metastasis. The aim of this study was to investigate the expression pattern of MMPs in the primary tumor of head and neck squamous cell carcinomas (HNSCC) with cervical node metastasis and to correlate the expression of MMP in the primary tumor with the presence of extracapsular spread (ECS) in nodes with metastasis. A retrospective study was conducted. Paraffin blocks were obtained from 40 HNSCC patients with cervical node metastasis who underwent surgery as an initial treatment between 2004 and 2011. Expressions of MMP-2, MMP-3, MMP-12, and MMP-14 were investigated immunohistochemically. MMP-2, MMP-3, MMP-12, and MMP-14 were expressed in 27, 47.5, 55, and 57.5 % of cases, respectively. MMP-12 expression was found to be significantly associated with ECS and correlated with nodal metastasis (p = 0.024, 0.011). No relation was found between MMP expression and survival. MMP-12 expressed in the primary tumor is a molecular marker that may be useful for predicting ECS in HNSCC patients with metastatic nodal disease.

Reconstruction of the head and neck region using lower trapezius musculocutaneous flaps.

BACKGROUND: Recent literature has indicated that free flaps are currently considered the preferred choice for head and neck reconstruction. However, head and neck cancer patients are frequently treated with chemoradiotherapy, which is often associated with a poor general and local condition, and thus, such patients are ineligible for free flap reconstruction. Therefore, other reconstruction modalities should be considered. METHODS: We used lower trapezius musculocutaneous (LTMC) flap based on the dorsal scapular artery to reconstruct head and neck defects that arose from head and neck cancer in 8 patients. All of the patients had undergone preoperative chemoradiotherapy. RESULTS: There were no complications except one case of partial flap necrosis; it was treated with secondary intention. Healing in the remaining patients was uneventful without hematoma, seroma, or infection. The donor sites were closed primarily. CONCLUSIONS: The LTMC flap is the preferred flap for a simple, reliable, large flap with a wide arc of rotation and minor donor-site morbidity. The authors recommend this versatile island flap as an alternative to microvascular free tissue transfer for the reconstruction of defects in the head and neck region, for patients that have undergone preoperative chemoradiotherapy.

Complete laryngotracheal separation following attempted hanging.

Laryngotracheal separation (LTS) is the most immediately life-threatening airway injury. LTS is so rare that very few otolaryngologists have experience with it. LTS is one of the diagnostic and therapeutic challenges in airway diseases and its management remains to be established. We experienced a patient with complete LTS after attempted hanging. A high index of suspicion, adequate imaging, prompt airway establishment and early surgical repair are the most vital factors in managing a patient with LTS.

Prediction of occult central lymph node metastasis in papillary thyroid carcinoma by preoperative BRAF analysis using fine-needle aspiration biopsy: a prospective study.

CONTEXT: Few reports have determined whether preoperative detection of the BRAF V600E mutation in fine-needle aspiration biopsy (FNAB) may influence determination of surgical extent such as prophylactic central lymph node dissection (CLND) in patients with papillary thyroid carcinoma (PTC). OBJECTIVES: Our objectives were to investigate whether preoperative BRAF analysis may assist determination of surgical extent, including prophylactic CLND with variable clinicopathological risk factors for central lymph node metastasis, in patients with PTC and clinically node-negative neck. PATIENTS AND METHODS: From July 2009 to May 2011, we prospectively enrolled 148 PTC patients with clinically node-negative neck who received a total thyroidectomy and prophylactic CLND. BRAF mutation by pyrosequencing was tested on preoperative FNAB specimens. The relationships between occult central lymph node metastasis and preoperative BRAF mutation or clinicopathological factors were analyzed. Additionally, we assessed the associations between preoperative BRAF mutation status and various clinicopathological characteristics of PTC revealed postoperatively. RESULTS: The prevalence of the BRAF V600E mutation was 53.4%, and the rate of occult central lymph node metastasis was 25.7%. Multivariate analysis showed that tumor size over 1 cm [P = 0.006; odds ratio (OR) = 3.559], perithyroidal invasion (P = 0.023; OR = 2.893), and preoperative positive BRAF mutation (P = 0.029; OR = 2.727) were independent risk factors for the presence of occult central lymph node metastasis. BRAF mutation examined in FNAB specimens, compared with the wild-type allele, strongly predicted perithyroidal invasion (48 vs. 29%; P = 0.017), extracapsular spread (65 vs. 45%; P = 0.017), occult central lymph node metastasis (35 vs. 15%; P = 0.004), and advanced TNM stage (44 vs. 28%; P = 0.035). In the multivariate analysis, patients with preoperative positive BRAF mutation were significantly more likely (P = 0.023; OR = 2.848) to have occult central lymph node metastasis. CONCLUSION: Preoperative BRAF analysis by FNAB and primary tumor size based on ultrasonography may assist in predicting occult central lymph node metastasis in patients with PTC and clinically node-negative neck.

Pattern of expression of cyclooxygenase-2 in malignant transformation of sinonasal inverted papilloma.

OBJECTIVE: Cyclooxygenases (COXs) are enzymes that catalyze the conversion of arachidonic acid to prostaglandins. Many studies have suggested that COX-2, the inducible form of COX, is important in carcinogenesis. However, little is known about the pattern of expression of COX-2 in a multistep process of malignant transformation of sinonasal inverted papilloma (IP). In this study, we investigated COX-2 expression in IPs, IPs with dysplasia, IPs with squamous cell carcinoma (SCC), and primary SCCs of sinonasal tract. STUDY DESIGN: A retrospective study was conducted. SETTING: The setting was a tertiary care referral center. SUBJECTS AND METHODS: The expression of COX-2 was evaluated by immunohistochemistry in 56, 7, 18, and 17 cases of IPs, IPs with dysplasia, IPs with SCC, and primary SCCs, respectively. Furthermore, we investigated the possible correlation between the expression of COX-2 and clinicopathologic variables in patients with IPs with SCC and primary SCC patients. RESULTS: Positive immunoreactivity for COX-2 was observed in 3 (5.4%) of 56 IPs, 7 (38.9%) of 18 IPs with SCC, and 7 (41.2%) of 17 primary SCCs, whereas it was not observed in IPs with dysplasia. The percentage of tumors with COX-2-positive immunostaining was significantly higher in IPs with SCC and primary SCCs compared with benign IPs. There was no significant correlation between the expression of COX-2 and clinicopathologic variables, such as tumor stage, histologic differentiation, and the proportion of malignant areas in patients with IPs with SCC. CONCLUSION: Cyclooxygenase-2 may play an important role in the process of malignant transformation from IP to SCC.

Clinical and histologic features of inverted papilloma-associated malignancy.

The objectives of the study were to analyze the clinical features of inverted papillomas (IP) associated with malignancy and to evaluate the correlation of tumor stage, survival and histolologic features. We conducted a retrospective review of 18 IP associated with malignancy patients. In addition, we compared histopathologic characteristics (tumor differentiation and malignant cell proportion) with clinical outcomes. Eleven of the tumors were present on the nasal cavity and 7 on the maxillary sinus. The rates of synchronous and metachronous malignancy were 10.1 and 1.1%, respectively. The disease-free survival rate was 83.3%. The tumors were staged as T1 (5/18), T2 (2/18), T3 (8/18), and T4 (3/18). According to the percentage of the malignant cell in the entire tumor tissue, 4 patients (22%) were in grade I, 4 patients (22%) were in grade II, 3 patients (17%) were in grade III, and 7 patients (39%) were in grade IV. There was no relationship between recurrence- and/or disease-free survival and histologic findings including tumor differentiation and malignant proportion. IP-associated malignancy tends to occur synchronously and have more favorable prognosis compared to other sinonasal malignancy. Furthermore, the proportion of malignant cell to IP and tumor stage seems not to affect the clinical outcome of IP-associated malignancy.

The clinicopathologic differences in papillary thyroid carcinoma with or without co-existing chronic lymphocytic thyroiditis.

The goal of this study is to determine the clinicopathologic differences in patients with papillary thyroid carcinoma (PTC) with or without chronic lymphocytic thyroiditis (CLT). We reviewed the medical records of 195 consecutive PTC patients who underwent total thyroidectomy and bilateral central lymph node dissection from April 2008 to March 2010. The differences in clinicopathologic factors, such as age, gender, size of primary tumor, perithyroidal invasion, lymphovascular invasion, capsular invasion, and central lymph node (CLN) metastasis, were analyzed in PTC patients with or without CLT. Among 195 patients, 56 (28.7%) had co-existing CLT. Patients with CLT had the following characteristics as compared to patients without CLT: significantly younger, female predominance, smaller tumor size, and lower incidence of capsular invasion (p = 0.038, 0.006, 0.037, and 0.026, respectively). Also, patients with CLT (12.5%) had a significantly lower incidence of CLN metastases than patients without CLT (28.1%; p = 0.025) based on univariate analysis. Moreover, multivariate analysis showed that younger age (p = 0.042, odds ratio = 1.033) and female gender (p = 0.012, odds ratio = 6.865) are independent clinical factors in patients with CLT compared to patients without CLT. CLT was shown to be commonly associated with PTC. Compared to patients with PTC without CLT, patients with CLT were younger with a female predominance, which are the most important and well-known prognostic variables for thyroid cancer mortality.

Selective dispersion of high purity semiconducting single-walled carbon nanotubes with regioregular poly(3-alkylthiophene)s.

Conjugated polymers, such as polyfluorene and poly(phenylene vinylene), have been used to selectively disperse semiconducting single-walled carbon nanotubes (sc-SWNTs), but these polymers have limited applications in transistors and solar cells. Regioregular poly(3-alkylthiophene)s (rr-P3ATs) are the most widely used materials for organic electronics and have been observed to wrap around SWNTs. However, no sorting of sc-SWNTs has been achieved before. Here we report the application of rr-P3ATs to sort sc-SWNTs. Through rational selection of polymers, solvent and temperature, we achieved highly selective dispersion of sc-SWNTs. Our approach enables direct film preparation after a simple centrifugation step. Using the sorted sc-SWNTs, we fabricate high-performance SWNT network transistors with observed charge-carrier mobility as high as 12 cm(2) V(-1) s(-1) and on/off ratio of >10(6). Our method offers a facile and a scalable route for separating sc-SWNTs and fabrication of electronic devices.

Is there any synergic effect for coadministration of mitomycin C and halofuginone on the skin wound healing?

OBJECTIVE: This study compared the potencies of the antifibrotic agents mitomycin C (MMC) and halofuginone (HFN) and investigated whether coadministration of these agents produces synergic effects in an animal skin wound model. SUBJECTS AND METHODS: Twenty male Sprague-Dawley rats were used for this study. After a full-thickness excisional wound was made on the dorsum of each rat, each rat was treated with topical mitomycin, intraperitoneal HFN, or both. Wound surface areas were measured over time, and histologic analysis was performed after wounds healed completely. RESULTS: The groups treated with MMC alone, HFN alone, and a combination of the two all exhibited delayed wound healing compared with the untreated group. Histologically, fibrosis and matrix metalloproteinase-2 expression were significantly inhibited in the treated groups. However, there were no gross or histologic differences between the MMC-treated group, the HFN-treated group, and the combination-treatment group. CONCLUSIONS: Both MMC and HFN inhibited excessive fibrosis. However, there was no significant difference in the antifibrotic effects of MMC and HFN on surgically induced skin wounds. Moreover, combination treatment with both MMC and HFN failed to confer an additional antifibrotic effect on skin wounds when compared with treatment with MMC or HFN alone.

Occult contralateral carcinoma in patients with unilateral papillary thyroid microcarcinoma.

BACKGROUND: The optimal resection extent for papillary thyroid microcarcinoma (PTMC) confined within a unilateral lobe remains controversial. MATERIALS AND METHODS: We reviewed the medical records of 132 consecutive patients who underwent total thyroidectomy for the treatment of clinically unilateral PTMC between March 2005 and March 2009. The frequency, pattern, and predictive factors for occult contralateral carcinoma in these patients were analyzed with respect to the following variables: age, gender, tumor size, multifocality of primary tumor, presence of perithyroidal invasion, lymphovascular invasion or capsular invasion, presence of central lymph node metastasis, and the presence of coexistent benign nodules in the contralateral lobe based on preoperative evaluation and final pathology. RESULTS: A total of 22 patients (16.7%) had occult PTMC in the contralateral lobe. In multivariate analysis, multifocality of the primary tumor (P = 0.026, odds ratio = 7.714) and the presence of coexistent benign nodule in the contralateral lobe by preoperative evaluation (P = 0.036, odds ratio = 3.500) were independent predictive factors for occult contralateral PTMC presence. However, there were no significant differences between the presence of occult contralateral carcinomas and age, gender, tumor size, perithyroidal invasion, lymphovascular invasion, capsular invasion, central lymph node metastasis, and coexistent benign nodules by final pathology. CONCLUSIONS: Based on our findings, total thyroidectomy, including the contralateral lobe, should be considered for the treatment of unilateral PTMC if it presents as a multifocal tumor in the unilateral lobe and/or if nodules are found in the contralateral lobe during preoperative evaluation.

Occult lymph node metastases in neck level V in papillary thyroid carcinoma.

BACKGROUND: The extent of lateral neck dissection for clinically evident nodal metastases in the lateral neck in a patient with papillary thyroid cancer (PTC) continues to remain controversial. METHODS: We reviewed retrospectively the medical records between March 2005 and March 2008 of 70 patients with PTC who underwent therapeutic lateral neck dissections (level II-V) to establish indications for omission of a level V lymphadenectomy. No patient in the study had a clinically positive level V lymph node. Neck dissection specimens were obtained for histologic analysis for node metastasis with respect to the individual neck levels. RESULTS: Thirty-four (49%), 52 (74%), and 48 (69%) patients had histologically positive lymph nodes in levels II, III, and IV, respectively. Occult metastases in level V were observed in 11 (16%) patients. Isolated positive level V lymph nodes were never found, while all patients with positive level V lymph nodes had simultaneous positive level IV lymph nodes. In addition, there was no instance of a pathologically positive lymph node in level V without a suspicious metastatic lymph node in level IV by preoperative ultrasonography. In multivariate analysis, simultaneous multilevel involvement (level II, III, and IV) of lymphatic metastases was associated with level V metastasis. CONCLUSION: Level V lymphadenectomy may be omitted in the treatment of PTC patients if positive nodes are not found on histologic exam (frozen section analysis) or by ultrasonography in level IV.

The preventive effect of mitomycin-C on the external auditory canal fibrosis in an experimentally induced animal model.

OBJECTIVE: The aim of this study was to investigate the preventive effect of mitomycin-C (MMC) on external auditory canal (EAC) fibrosis in an animal model. STUDY DESIGN: This is a randomized, controlled animal study. SUBJECTS AND METHODS: Sixteen guinea pigs were used for this study. After the skin of cartilaginous EAC was injured with an electrocautery, the cottonoid soaked in MMC solution with concentration of 0.4 mg/mL was topically applied for 5 minutes to the injured EAC in an MMC-treated group (n = 8). In addition, saline was applied in the control group (n = 8). At 4 weeks after injury, postsurgical changes of EAC were evaluated by histologic examination. RESULTS: External auditory canal fibrosis was induced by injury with electrocautery. The MMC-treated group showed less degree of fibrosis without differences in epithelialization and inflammatory cell infiltration. CONCLUSION: This study suggests that MMC can be helpful in preventing EAC fibrosis after injury.