A comparative study of quality of life in patients with papillary thyroid carcinoma undergoing microwave ablation vs. Total thyroidectomy.

OBJECTIVE: To compare the health-related quality of life (HRQoL) of patients with T1N0M0 papillary thyroid carcinoma (PTC) who underwent microwave ablation (MWA) and those who underwent total thyroidectomy (TT). MATERIALS AND METHODS: From February 2018 to February 2022, 180 T1N0M0 PTC patients were enrolled in present study, including 90 in the MWA group and 90 in the TT group, respectively. The European Organization for Research and Treatment of Cancer Quality of Life Questionnaire (EORTC QLQ-C30) and Thyroid Cancer-Specific Quality of Life Questionnaire (THYCA-QoL) were completed by patients to evaluate their HRQoL scores. RESULTS: According to the results of the EORTC-QLQ-C30, there was a significant difference in the scores of global health, physical, emotional, etc. between the two groups, which indicated that the quality of life in these items in the MWA group was better than those in the TT group (all p < 0.05). According to the results of the THYCA-QoL, all items had significant differences between the two groups except for headache, which demonstrated the thyroid-specific quality of life was higher in the MWA group than in the TT group (all p < 0.05). CONCLUSION: Ultrasound (US)-guided MWA offers a significant advantage in HRQoL over TT in T1N0M0 PTC patients, which provides an important reference for MWA as an alternative strategy to TT.

Strategies for Collection and Analysis of Samples in Simple Asphyxiant Gas Acute Poisoning Death Cases.

At present, the death cases of simple asphyxiant gas acute poisoning are increasing sharply. Common asphyxiant gases in death cases include nitrogen, helium, carbon dioxide, methane, propane, laughing gas, etc. Simple asphyxiant gas has no affinity for biological matrices and escapes quickly, which puts forward new requirements for autopsy procedures, selection and collection of samples, laboratory analysis and identification. This paper reviews the research and development process of death cases caused by simple asphyxiant gas acute poisoning and put forwards the collection and analysis strategy of the samples in such cases. The most valuable biological samples in such cases should be lung tissues associated with the airways, followed by brain tissue and cardiac blood. Gaseous samples from the esophageal cavity, tracheal cavity, pulmonary bronchi, gastric and cardiac areas are also recommended as valuable samples. In the case of postmortem examination, the gas should be injected into gas sample bag directly. Biological materials such as tissue and blood should be directly sealed in head-space vials and analyzed by using the headspace gas chromatography-mass spectrometry.

Forensic Analysis of 9 Poisoning Death Cases Caused by Oral Administration of Diphenidol.

OBJECTIVES: To analyze the characteristics of diphenidol poisoning cases and to provide clues and technical means for the identification of such cases. METHODS: Biological samples of 9 deaths caused by diphenidol poisoning were detected by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and the characteristics of these cases were analyzed retrospectively. RESULTS: Most of the deaths caused by diphenidol poisoning were young females. The dosage was between 60 and 300 tablets, and the mass concentration of diphenidol in the postmortem blood ranged from 0.87 to 99.00 µg/mL. There was no correlation between the dosage and the concentration of diphenidol in the blood. CONCLUSIONS: Diphenidol poisoning has the characteristics of high concealment and lethality. More attention should be paid to suicide cases, and diphenidol should be recommended as a routine detection item to avoid missing detection.

The Assessment of Sleep Quality in Patients Following Valve Repair and Valve Replacement for Infective Endocarditis: A Retrospective Study at a Single Center.

BACKGROUND The aim of this study was to measure sleep quality among patients who underwent infective endocarditis (IE) surgery and identify the risk factors involved in sleep disorders. MATERIAL AND METHODS In this study, we used actigraphy, the Pittsburgh Sleep Quality Index (PSQI), and Epworth Sleep Scale (ESS) to determine the clinical characteristics of sleep disorders in 116 patients with IE who were in rehabilitation after surgery. RESULTS Our results showed that 46 (39.7%) patients had sleep efficiency over 85%, while 70 (60.3%) patients had sleep efficiency below 85%. The correlation analysis showed that sleep efficiency was related to the duration of the disease, with a longer duration leading to lower sleep efficiency (P=0.031). The sleep efficiency of patients with IE following surgery was also affected by alcohol consumption; however, surprisingly, patients with "heavy" alcohol consumption had higher sleep efficiency (P=0.030). We found a significant correlation between sleep efficiency and postoperative interleukin-6 (IL) levels, C-reactive protein (CRP) levels, and preoperative erythrocyte sedimentation rate (P<0.05). No significant correlation was found between brain natriuretic peptide levels and sleep efficiency, PSQI score, or ESS score. Postoperative hemoglobin (Hb) level was associated with sleep efficiency (R=0.194, P=0.036), but there was no statistically significant correlation between the PSQI and ESS scores. Postoperative alanine transaminase (ALT) showed a significant negative correlation with sleep efficiency (R=-0.27, P=0.003). CONCLUSIONS We found a high prevalence of sleep disorders in patients with IE along with an increase in inflammatory factors, including postoperative IL-6, CRP, ALT, and Hb levels.

Immunogenicity of adenovirus and DNA vaccines co-expressing P39 and lumazine synthase proteins of Brucella abortus in BALB/c mice.

Brucella poses a great threat to animal and human health. Vaccination is the most promising strategy in the effort to control Brucella abortus (B. abortus) infection, but the currently used live vaccines interfere with diagnostic tests and could potentially result in disease outbreak. Therefore, new subunit vaccines and combined immunization strategies are currently under investigation. In this study, immunogenicity and protection ability of a recombinant adenovirus and plasmid DNA vaccine co-expressing P39 and lumazine synthase proteins of B. abortus were evaluated based on the construction of the two molecular vaccines. Four immunization strategies (single adenovirus, single DNA, adenovirus/DNA, DNA/adenovirus) were investigated. The results showed that the immunization strategy of DNA priming followed by adenovirus boosting induced robust humoral and cellular immune responses, and it significantly reduced the numbers of B. abortus in a mouse model. These results suggest that it could be a potential antigen candidate for development of a new subunit vaccine against B. abortus infection.

Effect of acupotomy combined with electroacupuncture on knee function of patients with knee osteoarthritis. / åˆƒé’ˆç»“åˆç”µé’ˆæ²»ç–—å¯¹è†å ³èŠ‚éª¨å ³èŠ‚ç‚Žæ‚£è€ è†å ³èŠ‚åŠŸèƒ½çš„å½±å“.

OBJECTIVES: To compare the clinical effect of combined therapy of acupotomy and electroacupuncture (EA) with the simple application of EA on knee osteoarthritis (KOA), and their influence on knee function. METHODS: Sixty-eight KOA patients were randomly divided into 2 groups, an acupotomy group and an EA group. In the acupotomy group, the combined therapy of acupotomy and EA was adopted. In the EA group, EA was simply used, delivered once every two days, 3 treatments a week；and the duration of treatment was 4 weeks. In the acupotomy group, besides the treatment as the EA group, acupotomy was combined once weekly, and the duration of treatment was 4 weeks. Separately, before and after treatment, and in 4 and 12 weeks after treatment completion (1-month and 3-month follow-up), the results of the timed up and go test (TUG), the 9-step stair climb test (9-SCT) and the knee function (Western Ontario and McMaster University osteoarthritis index visualization scale ［WOMAC］) were measured in the two groups. RESULTS: By the intention-to-treat analysis, the results of TUG, 9-SCT and WOMAC scores were reduced after treatment and in 1-month and 3-month follow-up when compared with those before treatment in the patients of the two groups (P<0.05). Compared with the EA group at the same time point, TUG results were decreased after treatment and in 1-month follow-up, and WOMAC score was reduced after treatment in the acupotomy group. WOMAC score in 1-month follow-up was reduced when compared with that before treatment within the acupotomy group (P<0.05). CONCLUSIONS: Either the simple application of EA or the combined therapy of acupotomy and EA can improve knee function, but the combined therapy obviously increases the walking speed and relieves the symptoms such as joint pain and morning stiffness. The treatment with acupotomy and EA is safe and effective on KOA and the long-term effect is satisfactory.

Optimization of fermentation medium for the production of atrazine degrading strain Acinetobacter sp. DNS(32) by statistical analysis system.

Statistical experimental designs provided by statistical analysis system (SAS) software were applied to optimize the fermentation medium composition for the production of atrazine-degrading Acinetobacter sp. DNS(32) in shake-flask cultures. A "Plackett-Burman Design" was employed to evaluate the effects of different components in the medium. The concentrations of corn flour, soybean flour, and K(2)HPO(4) were found to significantly influence Acinetobacter sp. DNS(32) production. The steepest ascent method was employed to determine the optimal regions of these three significant factors. Then, these three factors were optimized using central composite design of "response surface methodology." The optimized fermentation medium composition was composed as follows (g/L): corn flour 39.49, soybean flour 25.64, CaCO(3) 3, K(2)HPO(4) 3.27, MgSO(4)·7H(2)O 0.2, and NaCl 0.2. The predicted and verifiable values in the medium with optimized concentration of components in shake flasks experiments were 7.079 × 10(8) CFU/mL and 7.194 × 10(8) CFU/mL, respectively. The validated model can precisely predict the growth of atrazine-degraing bacterium, Acinetobacter sp. DNS(32).

Sleep patterns and potential risk factors for disturbed sleep quality in patients after surgery for infective endocarditis.

BACKGROUND: The current study aimed to investigate the sleep quality of patients after valve replacement surgery due to infective endocarditis and identify risk factors for disturbed sleep post hospitalisation. METHODS: Eighty patients were assessed postoperatively using subjective scale measures, the Pittsburgh sleep quality index (PSQI) and the Epworth sleepiness scale, and an objective measure, actigraphy. Scale measures were assessed approximately 2 weeks and 6 months after surgery. Actigraphy monitoring was performed for 2 consecutive weeks during hospitalisation. Logistic regression was used to identify risk factors for disturbed sleep. RESULTS: The study population (n = 80) had an average age of 42.8 ± 14.2 years, and 67.5% were male. The median sleep efficiency was 85.3% in week 1 and 86.8% in week 2. The frequency of awakenings was significantly higher in week 1 (20.0 times vs. 19.3 times, p = 0.017). The scale measures showed significant improvement in sleep by 6 months after surgery compared to that during hospitalisation. Multivariable logistic regression analysis suggested that the possible risk factors for disturbed sleep 6 months after surgery included age (OR = 1.479, 95%CI 1.140-1.920) and a few parameters of early postoperative disturbed sleep quality (PSQI: OR = 2.921, 95%CI 1.431-5.963; sleep efficiency: OR = 0.402, 95%CI 0.206-0.783; and average duration of awakenings: OR = 0.006, 95%CI 0.000-0.827). CONCLUSIONS: Disturbed sleep quality was witnessed in postoperative patients during hospitalisation and up to 6 months after surgery. Over time, the patients' sleep quality improved significantly. Age and a few early postoperative sleep quality variables were risk factors for disturbed sleep 6 months after surgery.

Habitat selection of black-and-white snub-nosed monkeys (Rhinopithecus bieti) in Tibet: implications for species conservation.

As anthropogenic habitat changes are often considered a threat to natural ecosystems and wildlife, a sound understanding of the effects of habitat alteration on endangered species is crucial when designing management strategies or performing conservation activities. Black-and-white snub-nosed monkeys (Rhinopithecus bieti) are categorized as endangered on the IUCN Red List and are endemic to the trans-Himalayas in China. At present, there are only 15 groups and 2,500 individuals remaining in the wild, and they are facing intense habitat degradation with selective logging for house building and firewood. Habitat deterioration through wood extraction is occurring at Xiaochangdu, Tibet, where one stable group of R. bieti lives in a marginal habitat in the northernmost part of the species' distribution. To understand the species' response to selective logging in an extremely marginal habitat, data on habitat preference and diet composition of a group of R. bieti were collected at Xiaochangdu from 2003 to 2005. The monkeys used different habitats nonrandomly during the year. The selection index for secondary conifer forest (SC), where selective logging has occurred, was the highest of all habitat types (>1), suggesting that the groups strongly preferred SC. The monkeys fed more on buds/leaves, more on flowers/fruit/seeds, and less on lichen in SC than in primary conifer forest (PC). Dietary diversity was significantly higher in SC than in PC. These results indicate that over the short term, low-intensity disturbances may result in increased foliage diversity that enable groups of R. bieti to survive in this marginal habitat.

Radiotherapy of unicentric mediastinal Castleman's disease.

Castleman's disease is a slowly progressive and rare lymphoproliferative disorder. Here, we report a 55-year-old woman with superior mediastinal Castleman's disease being misdiagnosed for a long term. We found a 4.3 cm mass localized in the superior mediastinum accompanied with severe clinical symptoms. The patient underwent an exploratory laparotomy, but the mass failed to be totally excised. Pathologic examination revealed a mediastinal mass of Castleman's disease. After radiotherapy of 30 Gy by 15 fractions, the patient no longer presented previous symptoms. At 3 months after radiotherapy of 60 Gy by 30 fractions, Computed tomography of the chest showed significantly smaller mass, indicating partial remission. Upon a 10-month follow-up, the patient was alive and free of symptoms.

[Surgical anatomy of totally trans-oral video-assisted thyroidectomy].

OBJECTIVE: To define the anatomical approach, anatomical planes and related vessels and nerves to create a safe and reproducible combined sublingual and bi-vestibular access for trans-oral video-assisted thyroidectomy. METHODS: From November 2009 to May 2011, twenty-five embalmed human specimens were dissected for anatomical information of the cervical region, the mandible region and the supra-hyoid muscles. On twenty fresh frozen human specimens after an experimental trans-oral endoscopic thyroidectomy, the related vascular, neural structures and muscles were evaluated. RESULTS: The optical access port was placed in the midline sublingual. The geniohyoid muscle, mylohyoid muscle and the anterior belly of the digastric muscle were divided in the midline in order to reach the plane under the platysma muscle. The mucosa was sagittal incised bilaterally in the vestibular of oral cavity for working trocar, at the level of the first molar of the mandible. The working trocar reached directly the periosteum of the mandible, under the facial vessel and the marginal branch of facial nerve, and then passed below the platysma muscle into the infra-laryngeal working area. The distance from mental nerve to mandibular midline and between mental nerve and facial artery were (25.8 ± 0.9) mm and (29.4 ± 0.9) mm respectively. Anatomical dissections showed that after an experimental trans-oral combined sublingual and bi-vestibular access, all muscles of the floor of the oral cavity as well as the related vascular and neural structures are intact. The maximum nodule size of the resected specimens in the totally trans-oral approach was up to 50 mm. CONCLUSION: The combined sublingual and bi-vestibular access of trans-oral video-assisted thyroidectomy is safe and reproducible.

Analysis of sleep characteristics and clinical outcomes of 139 adult patients with infective endocarditis after surgery.

BACKGROUND: Little is known about the postoperative sleep quality of infective endocarditis patients during hospitalization and after discharge. AIM: To investigate the sleep characteristics of infective endocarditis patients and to identify potential risk factors for disturbed sleep quality after surgery. METHODS: The Pittsburgh Sleep Quality Index (PSQI) and the Epworth Sleepiness Scale were used to assess patient sleep quality. Logistic regression was used to explore the potential risk factors. RESULTS: The study population (n = 139) had an average age of 43.40 ± 14.56 years, and 67.6% were men (n = 94). Disturbed sleep quality was observed in 86 patients (61.9%) during hospitalization and remained in 46 patients (33.1%) at 6 mo after surgery. However, both PSQI and Epworth Sleepiness Scale scores showed significant improvements at 6 mo (P < 0.001 and P = 0.001, respectively). Multivariable logistic regression analysis showed that the potential risk factors were age (odds ratio = 1.125, 95% confidence interval: 1.068-1.186) and PSQI assessed during hospitalization (odds ratio = 1.759, 95% confidence interval: 1.436-2.155). The same analysis in patients with PSQI ≥ 8 during hospitalization suggested that not using sleep medication (odds ratio = 15.893, 95% confidence interval: 2.385-105.889) may be another risk factor. CONCLUSION: The incidence of disturbed sleep after infective endocarditis surgery is high. However, the situation improves significantly over time. Age and early postoperative high PSQI score are risk factors for disturbed sleep quality at 6 mo after surgery.

Exploring electrosorption at iron electrode with in situ surface-enhanced infrared absorption spectroscopy.

Surface-enhanced infrared absorption spectroscopy (SEIRAS) in attenuated total reflection (ATR) configuration has been extended to the Fe electrode/electrolyte interface in neutral and weakly acidic solutions for the first time. The SEIRA-active Fe film electrode was obtained through a potentiostatic electrodeposition of a virtually pinhole-free 40 nm-thick Fe overfilm onto a 60 nm-thick Au underfilm chemically predeposited on the reflecting plane of an ATR Si prism. The infrared absorption for CO adlayer at the Fe film electrode measured with ATR-SEIRAS was enhanced by a factor of larger than 34, as compared to that at a Fe bulk electrode with external infrared absorption spectroscopy in the literature. More importantly, the unipolar band shape enabled the reliable determination of the Stark tuning rates of CO adlayer at Fe electrode. In situ ATR-SEIRAS was also applied to study the electrosorption of a typical corrosion inhibitor benzotriazole (BTAH) on Fe electrode as a function of potential, providing additional spectral information at positive potentials in support of the formation of a polymer-like surface complex Fe(II)(m)(BTA)(n) as the corrosion-resistant layer.

Expression profiling of a novel calcium-dependent protein kinase gene, LeCPK2, from tomato (Solanum lycopersicum) under heat and pathogen-related hormones.

A full-length cDNA LeCPK2 (GenBank GQ205414) from tomato (Solanum lycopersicum) encoding a calcium-dependent protein kinase (CDPK) was cloned by in silico cloning using NtCPK5 (AY971376) as a virtual probe. The deduced amino acid sequence of LeCPK2 contained the kinase, autoinhibitory, and calmodulin-like domains typical of CDPKs. Expression profiling indicated that LeCPK2 expressed predominantly in flowers and responded divergently to heat and cold stress, in which obvious mRNA accumulation was detected at 4 h under 42 degrees C stress, but no change in LeCPK2 mRNA levels was observed in 6 h at 4 degrees C. Mechanical wounding and phytohormones including ethylene, methyl jasmonate, and salicylic acid were also observed to arouse the expression of LeCPK2 in a similar pattern. mRNA accumulation was enhanced at 30 min and reached a maximum at 3 h, followed by a decrease to the normal level. All the results suggest that LeCPK2 is a novel versatile isoform of tomato CDPKs.

Singing behavior and singing functions of black-crested gibbons (Nomascus concolor jingdongensis) at Mt. Wuliang, central Yunnan, China.

We used data on loud duetted and solo songs collected from one habituated polygynous group of black-crested gibbons (Nomascus concolor jingdongensis) on Mt. Wuliang, Yunnan, to test several hypotheses about the functions of these songs. The major functions proposed for loud gibbon songs include resource defense, mate defense, pairbonding, group cohesion and mate attraction. Duet bouts are generally initiated by adult males, who select the highest trees near to ridges or on steep slopes as singing trees. Such trees facilitate voice transmission and inter-group communication. Singing trees tended to be located near important food patches and sleeping sites, which supports the resource defense hypothesis. The adult male and two adult females always sang interactively, alternating male phrases with the females' stereotyped great calls, to produce the duets, and females rarely produced great calls if they were more than 30 m from the male. The two females usually produced great calls synchronously during the duet, especially when they were close together. These features support both the mate defense and pairbonding hypotheses. The number of great calls and their degree of synchrony transmit information about spatial relationships and possibly pairbond strength to members to neighboring groups and floating animals. During or after the duet bouts, the adult females and juvenile moved toward to the adult male; and group members maintained a close spatial relationship, which supports the group cohesion hypothesis. Other incidents observed suggest a mate competition role for duets. The adult male always sang when the females started duetting with the subadult male. The subadult male sang solo bouts, but they were not more frequent or longer than bouts initiated by the adult male. Although mate attraction is the likely function of subadult solos, it was not convincingly demonstrated. In conclusion, all hypotheses concerning the function of singing are supported by at least some of the data, and none can be excluded.

[Association between CD4+CD25+Foxp3+ regulatory T cells and serum transforming growth factor beta 1 in patients with chronic hepatitis B].

OBJECTIVE: To investigate whether the CD4+CD25+Foxp3+ regulatory T cells are associated with serum TGF beta 1 in patients with hepatitis B. METHODS: Patients with chronic hepatitis B (CHB), chronic asymptomatic carriers (AsC), normal subjects (NS) and the resolved from HBV infection (Resolved) were recruited in this study. Flow cytometric analysis was used to detect the frequency and phenotype of peripheral CD4+CD25+Foxp3+ T cells, and Foxp3 gene expression were examined by real time PCR. Serum TGF beta 1 levels were measured by ELISA (enzyme-linked immunosorbent assay). RESULTS: Patients with CHB or AsC exhibited significantly higher frequency of CD4+CD25+Foxp3+ T cells compared to healthy controls. CD4+CD25+ T cells derived from patients with CHB and AsC expressed higher level of Foxp3-mRNA. Furthermore, the frequency of CD4+CD25+Foxp3+ regulatory T cells was correlated with serum HBV DNA copy numbers in patients with CHB and AsC. Our results indicated that the serum TGF beta was increased in CHB and AsC patients compared to control patients, and that serum TGF beta was correlated with the expression of Foxp3-mRNA and the frequency of CD4+CD25+Foxp3+ regulatory T cells in patients with CHB and AsC. CONCLUSIONS: The findings have important implication in the understanding of the role and mechanism of aberrant CD4+CD25+Foxp3+ regulatory T cells in the maintenance of chronicity in hepatitis B patients.

Developing a DNA barcode library for perciform fishes in the South China Sea: Species identification, accuracy and cryptic diversity.

DNA barcodes were studied for 1,353 specimens representing 272 morphological species belonging to 149 genera and 55 families of Perciformes from the South China Sea (SCS). The average Kimura 2-parameter (K2P) distances within species, genera and families were 0.31%, 8.71% and 14.52%, respectively. A neighbour-joining (NJ) tree, Bayesian inference (BI) and maximum-likelihood (ML) trees and Automatic Barcode Gap Discovery (ABGD) revealed 260, 253 and 259 single-species-representing clusters, respectively. Barcoding gap analysis (BGA) demonstrated that barcode gaps were present for 178 of 187 species analysed with multiple specimens (95.2%), with the minimum interspecific distance to the nearest neighbour larger than the maximum intraspecific distance. A group of three Thunnus species (T. albacares, T. obesus and T. tonggol), a pair of Gerres species (G. oyena and G. japonicus), a pair of Istiblennius species (I. edentulous and I. lineatus) and a pair of Uranoscopus species (U. oligolepis and U. kaianus) were observed with low interspecific distances and overlaps between intra- and interspecific genetic distances. Three species (Apogon ellioti, Naucrates ductor and Psenopsis anomala) showed deep intraspecific divergences and generated two lineages each, suggesting the possibility of cryptic species. Our results demonstrated that DNA barcodes are highly reliable for delineating species of Perciformes in the SCS. The DNA barcode library established in this study will shed light on further research on the diversity of Perciformes in the SCS.

Seeded-growth approach to fabrication of silver nanoparticle films on silicon for electrochemical ATR surface-enhanced IR absorption spectroscopy.

Ag nanoparticle films (simplified as nanofilms hereafter) on Si for electrochemical ATR surface enhanced IR absorption spectroscopy (ATR-SEIRAS) have been successfully fabricated by using chemical deposition, which incorporates initial embedding of Ag seeds on the reflecting plane of an ATR Si prism and subsequent chemical plating of conductive and SEIRA-active Ag nanofilms. Two alternative methods for embedding initial Ag seeds have been developed: one is based on self-assembly of Ag colloids on an aminosilanized Si surface, whereas the other the reduction of Ag+ in a HF-containing solution. A modified silver-mirror reaction was employed for further growth of Ag seeds into Ag nanofilm electrodes with a theoretically average thickness of 40-50 nm. Both Ag seeds and as-deposited Ag nanofilms display island structure morphologies facilitating SEIRA, as revealed by AFM imaging. The cyclic voltammetric feature of the as-prepared Ag nanofilm electrodes is close to that of a polycrystalline bulk Ag electrode. With thiocyanate as a surface probe, enhancement factors of ca. 50-80 were estimated for the as-deposited Ag nanofilms as compared to a mechanically polished Ag electrode in the conventional IRAS after reasonable calibration of surface roughness factor, incident angles, surface coverage, and polarization states. As a preliminary example for extended application, the pyridine adsorption configuration at an as-deposited Ag electrode was re-examined by ATR-SEIRAS. The results revealed that pyridine molecules are bound via N end to the Ag electrode with its ring plane perpendicular or slightly tilted to the local surface without rotating its C2 axis about the surface normal, consistent with the conclusion drawn by SERS in the literature.

In situ surface-enhanced IR absorption spectroscopy on CO adducts of iron protoporphyrin IX self-assembled on a Au electrode.

The surface coordination chemistry of carbon monoxide with the reduced form (Fe(II)PP) of iron(III) protoporphyrin IX (Fe(III)PP) monolayer self-assembled on a Au electrode in 0.1 M HClO4 was studied for the first time by using in situ ATR-surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). Both mono- and biscarbonyl adducts [simplified as Fe(II)(CO)PP and Fe(II)(CO)2PP, respectively] were detected, depending on the history of potential control. Initially, the Fe(II)(CO)PP predominates, and the intermediate transition potential for the conversion of Fe(II)(CO)PP to Fe(III)PP and CO was spectrally determined to be ca. 0.09 V (vs SCE). The ratio of Fe(II)(CO)2PP and Fe(II)(CO)PP increases after a potential excursion to a sufficiently positive value. Fe(II)(CO)2PP is much more stable against its electro-oxidation to Fe(III)PP than its counterpart Fe(II)(CO)PP with increasing potential. The observed change of coordination properties may be ascribed to an irreversible structural reorganization of the FePP adlayer caused by the potential excursion.

Extending in situ attenuated-total-reflection surface-enhanced infrared absorption spectroscopy to ni electrodes.

Surface-enhanced infrared absorption spectroscopy (SEIRAS) in the attenuated-total-reflection configuration (ATR-SEIRAS) has been applied for the first time to Ni electrodes. SEIRA-active Ni electrodes were obtained through initial chemical deposition of a 60-nm-thick Au underlayer on the reflecting plane of an ATR Si prism followed by potentiostatic electrodeposition of a 40-nm-thick Ni overlayer in a modified Watt's electrolyte. The Ni nanoparticle film thus obtained exhibited exceptionally enhanced IR absorption for the surface probe molecule CO while maintaining unipolar and normally directed bands. With the advantages of ATR-SEIRAS, free H2O molecules coadsorbed with CO at the Ni electrode were revealed, and their role in the electrooxidation of the CO adlayer at the Ni electrode is discussed. In addition, the conversion of bridge to linearly bonded CO at Ni electrode in a neutral solution was clearly identified upon electrooxidation of the CO adlayer. ATR-SEIRAS was also used to characterize the adsorption configuration of a pyridine adlayer at the Ni electrode. Both A1 and B1 modes of adsorbed pyridine were detected with comparably large intensities, essentially maintaining the spectral feature of pyridine molecules rather than that of "alpha-pyridyl species", which strongly suggests an "edge-tilted pyridine" configuration present at the Ni electrode, a configuration intermediate between the "end-on pyridine" and "edge-on alpha-pyridyl" adsorption modes reported in the literature.