Why Is Surface-Enhanced Raman Scattering Insensitive to Liquid Water?

Surface-enhanced Raman scattering (SERS) is widely recognized as a remarkably powerful analytical technique that enables trace-level detection of organic molecules on a metal surface in aqueous systems with negligible spectral interference of water. This insensitivity of SERS to liquid water is violated in a restrictive manner under specific electrochemical conditions. However, the origin of such different SERS sensitivities to liquid water remains unclear. Here, we show that hydrogen-bond networks of water play a pivotal role in losing SERS enhancement for liquid water, and SERS detection of water requires local defects in the hydrogen-bond networks, which are formed around hydration shells of solute ions or on a polarized electrode surface. This work gives a new perspective on in situ SERS investigations in aqueous systems, including electrochemical and biological reactions.

Molecular Self-Assembly and Adsorption Structure of 2,2'-Dipyrimidyl Disulfides on Au(111) Surfaces.

The effects of solution concentration and pH on the formation and surface structure of 2-pyrimidinethiolate (2PymS) self-assembled monolayers (SAMs) on Au(111) via the adsorption of 2,2'-dipyrimidyl disulfide (DPymDS) were examined using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). STM observations revealed that the formation and structural order of 2PymS SAMs were markedly influenced by the solution concentration and pH. 2PymS SAMs formed in a 0.01 mM ethanol solution were mainly composed of a more uniform and ordered phase compared with those formed in 0.001 mM or 1 mM solutions. SAMs formed in a 0.01 mM solution at pH 2 were composed of a fully disordered phase with many irregular and bright aggregates, whereas SAMs formed at pH 7 had small ordered domains and many bright islands. As the solution pH increased from pH 7 to pH 12, the surface morphology of 2PymS SAMs remarkably changed from small ordered domains to large ordered domains, which can be described as a (4√2 × 3)R51° packing structure. XPS measurements clearly showed that the adsorption of DPymDS on Au(111) resulted in the formation of 2PymS (thiolate) SAMs via the cleavage of the disulfide (S-S) bond in DPymDS, and most N atoms in the pyrimidine rings existed in the deprotonated form. The results herein will provide a new insight into the molecular self-assembly behaviors and adsorption structures of DPymDS molecules on Au(111) depending on solution concentration and pH.

Formation and Thermal Stability of Ordered Self-Assembled Monolayers by the Adsorption of Amide-Containing Alkanethiols on Au(111).

We examined the surface structure, binding conditions, electrochemical behavior, and thermal stability of self-assembled monolayers (SAMs) on Au(111) formed by N-(2-mercaptoethyl)heptanamide (MEHA) containing an amide group in an inner alkyl chain using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) to understand the effects of an internal amide group as a function of deposition time. The STM study clearly showed that the structural transitions of MEHA SAMs on Au(111) occurred from the liquid phase to the formation of a closely packed and well-ordered ß-phase via a loosely packed α-phase as an intermediate phase, depending on the deposition time. XPS measurements showed that the relative peak intensities of chemisorbed sulfur against Au 4f for MEHA SAMs formed after deposition for 1 min, 10 min, and 1 h were calculated to be 0.0022, 0.0068, and 0.0070, respectively. Based on the STM and XPS results, it is expected that the formation of a well-ordered ß-phase is due to an increased adsorption of chemisorbed sulfur and the structural rearrangement of molecular backbones to maximize lateral interactions resulting from a longer deposition period of 1 h. CV measurements showed a significant difference in the electrochemical behavior of MEHA and decanethiol (DT) SAMs as a result of the presence of an internal amide group in the MEHA SAMs. Herein, we report the first high-resolution STM image of well-ordered MEHA SAMs on Au(111) with a (3 × 2√3) superlattice (ß-phase). We also found that amide-containing MEHA SAMs were thermally much more stable than DT SAMs due to the formation of internal hydrogen networks in MEHA SAMs. Our molecular-scale STM results provide new insight into the growth process, surface structure, and thermal stability of amide-containing alkanethiols on Au(111).

Current status of umbilical cord blood storage and provision to private biobanks by institutions handling childbirth in Japan.

BACKGROUND: The Act Regarding the Promotion of the Appropriate Supply of Hematopoietic Stem Cells for Transplant regulates only how public banks store and provide umbilical cord blood (UCB) for research or transplantation. Japan had no laws to regulate how the private banks manage the procedures, harvesting, preparation, and storage of such blood. As a result, the status of UCB distribution remains unknown. We conducted a survey to investigate the current status of UCB storage and provision to private biobanks by Japanese institutions that handle childbirth. METHODS: Questionnaire forms were mailed to 3,277 facilities handling childbirth that were registered in the Japan Council for Quality Health Care website. RESULTS: Of the 1,192 institutions handling childbirth that participated in the survey (response rate: 36.7%), 34.4% responded that they currently provide UCB to private biobanks, while 16.1% of facilities did so in the past. Moreover, some institutions currently provide or formerly provided UCB to medical treatment facilities (2.6%), research institutions (5.9%), companies (2.2%), or overseas treatment facilities, research institutions, or companies (0.3%). A certain number of institutions handling childbirth did not even provide explanations or obtain consent when the UCB was harvested from private bank users. CONCLUSIONS: This is the first study to determine the status of UCB provision to private banks by Japanese institutions handling childbirth. Future studies will need to examine in detail how institutions handling childbirth provide explanations to private bank users and UCB providers as well as how these institutions obtain consent.

Analysis of Vicinal Water in Soft Contact Lenses Using a Combination of Infrared Absorption Spectroscopy and Multivariate Curve Resolution.

In this paper, we propose a new spectroscopic method to explore the behavior of molecules near polymeric molecular networks of water-containing soft materials such as hydrogels. We demonstrate the analysis of hydrogen bonding states of water in the vicinity of hydrogels (soft contact lenses). In this method, we apply force to hydrated contact lenses to deform them and to modulate the ratio between the signals from bulk and vicinal regions. We then collect spectra at different forces. Finally, we extracted the spectra of the vicinal region using the multivariate curve resolution-alternating least square (MCR-ALS) method. We report the hydration states depending on the chemical structures of hydrogels constituting the contact lenses.

Reuse of cardiac organs in transplantation: an ethical analysis.

BACKGROUND: This paper examines the ethical aspects of organ transplant surgery in which a donor heart is transplanted from a first recipient, following determination of death by neurologic criteria, to a second recipient. Retransplantation in this sense differs from that in which one recipient undergoes repeat heart transplantation of a newly donated organ, and is thus referred to here as "reuse cardiac organ transplantation." METHODS: Medical, legal, and ethical analysis, with a main focus on ethical analysis. RESULTS: From the medical perspective, it is critical to ensure the quality and safety of reused organs, but we lack sufficient empirical data pertaining to medical risk. From the legal perspective, a comparative examination of laws in the United States and Japan affirms no illegality, but legal scholars disagree on the appropriate analysis of the issues, including whether or not property rights apply to transplanted organs. Ethical arguments supporting the reuse of organs include the analogous nature of donation to gifts, the value of donations as inheritance property, and the public property theory as it pertains to organs. Meanwhile, ethical arguments such as those that address organ recycling and identity issues challenge organ reuse. CONCLUSION: We conclude that organ reuse is not only ethically permissible, but even ethically desirable. Furthermore, we suggest changes to be implemented in the informed consent process prior to organ transplantation. The organ transplant community worldwide should engage in wider and deeper discussions, in hopes that such efforts will lead to the timely preparation of guidelines to implement reuse cardiac organ transplantation as well as reuse transplantation of other organs such as kidney and liver.

Responsibility for reporting patient death due to hospital error in Japan when an error occurred at a referring institution.

In Japan, physicians are required to report unexpected health care-associated patient deaths to the police. Patients needing to be transferred to another institution often have complex medical problems. If a medical error occurs, it may be either at the final or the referring institution. Some fear that liability will fall on the final institution regardless of where the error occurred or that the referring facility may oppose such reporting, leading to a failure to report to police or to recommend an autopsy. Little is known about the actual opinions of physicians and risk managers in this regard. The authors sent standardised, self-administered questionnaires to all hospitals in Japan that participate in the national general residency program. Most physicians and risk managers in Japan indicated that they would report a patient's death to the police where the patient has been transferred. Of those who indicated they would not report to the police, the majority still indicated they would recommend an autopsy

Attitudes toward clinical autopsy in unexpected patient deaths in Japan: a nation-wide survey of the general public and physicians.

CONTEXT: Autopsy is a useful tool for understanding the cause and manner of unexpected patient death. However, the attitudes of the general public and physicians in Japan about clinical autopsy are limited. OBJECTIVE: To describe the beliefs of the general public about whether autopsy should be performed and ascertain if they would actually request one given specific clinical situations where patient death occurred with the additional variable of medical error. To compare these attitudes with previously obtained attitudes of physicians practising at Japanese teaching hospitals. DESIGN, SETTING AND PARTICIPANTS: We conducted a cross-sectional study of the general public. We sent standardised questionnaires in 2010 to a randomly selected non-physician adult population using a survey company for participant selection. Respondents gave their opinions about the necessity of autopsy and how they might act given various clinical scenarios of patient death. We compared these results with those of a previous survey of Japanese physicians conducted in 2009. RESULTS: Of the 2300 eligible general adult population, 1575 (68.5%) responded. The majority of the general public indicated they believed an autopsy was necessary. However, in cases of unclear medical error or unclear cause and effect relationship of medical care and patient death, the general public were much less likely to indicate they would actually request an autopsy than were physicians (p<0.0001). Currently in Japan the debate about the role autopsy should play in the case of error related to death is underway. The results from this study will be important in informing related decisions.

An Exploratory Study on Information Manipulation by Doctors: Awareness, Actual State, and Ethical Tolerance.

(1) Background: To what extent is information manipulation by doctors acceptable? To answer this question, we conducted an exploratory study aimed at obtaining basic data on descriptive ethics for considering this issue. (2) Methods: A self-administered questionnaire survey was conducted on a large sample (n = 3305) of doctors. The participants were queried on (1) whether they consider that information manipulation is necessary (awareness), (2) whether they have actually manipulated information (actual state), and (3) their ethical tolerance. (3) Result: The response rate was 28.7%. Sixty percent of the doctors responded that information manipulation to avoid harm to patients is necessary (awareness), that they have actually manipulated information (actual state), and that information manipulation is ethically acceptable. (4) Conclusion: While the present survey was conducted among doctors in Japan, previous studies have reported similar findings in the United States and Europe. Based on our analysis, we hypothesize that a relationship of trust between patients and medical personnel is crucial and that information manipulation is not needed when such a relationship has been established.

Prediction of Serum Adsorption onto Polymer Brush Films by Machine Learning.

Using machine learning based on a random forest (RF) regression algorithm, we attempted to predict the amount of adsorbed serum protein on polymer brush films from the films' physicochemical information and the monomers' chemical structures constituting the films using a RF model. After the training of the RF model using the data of polymer brush films synthesized from five different types of monomers, the model became capable of predicting the amount of adsorbed protein from the chemical structure, physicochemical properties of monomer molecules, and structural parameters (density and thickness of the films). The analysis of the trained RF quantitatively provided the importance of each structural parameter and physicochemical properties of monomers toward serum protein adsorption (SPA). The ranking for the significance of the parameters agrees with our general understanding and perception. Based on the results, we discuss the correlation between brush film's physical properties (such as thickness and density) and SPA and attempt to provide a guideline for the design of antibiofouling polymer brush films.

Doctor as criminal: reporting of patient deaths to the police and criminal prosecution of healthcare providers in Japan.

BACKGROUND: In Japan, medical error leading to patient death is often handled through the criminal rather than civil justice system. However, the number of cases handled through the criminal system and how this has changed in recent years has not previously been described. Our aim was to determine the trend in reports of patient death to the police and the trend in the resulting prosecution of healthcare providers for medical error leading to patient death from 1998 to 2008. METHODS: We collected data regarding the number of police reports of patient death made by physicians, next-of-kin, and other sources between 1998 and 2008. We also collected data regarding the number of resulting criminal prosecutions of healthcare providers between 1998 and 2008. Reporting and prosecution trends were analyzed using annual linear regression models. REPORTS: The number physician reports of patient deaths to the police increased significantly during the study period (slope 18.68, R2 = 0.78, P < 0.001) while reports made by next-of-kin and others did not. Mean annual reporting rates by group were physicians 130.1 (+/- 70.1), next-of-kin 29.3 (+/- 12.5), and others 10.4 (+/- 6.0). Prosecutions: The number of resulting criminal prosecutions increased significantly during the study period (slope 9.21, R2 = 0.83, P < 0.001). The mean annual prosecution rate was 61.0 (+/- 33.6). CONCLUSIONS: The reporting of patient deaths to the police by physicians increased significantly from 1998 to 2008 while those made by next-of-kin and others did not. The resulting criminal prosecutions of healthcare providers increased significantly during the same time period. The reasons for these increases are unclear and should be the focus of future research.

Attitudes toward autopsy in unexpected death: a nationwide survey of physicians and risk managers in Japanese teaching hospitals.

CONTEXT: Autopsy is a useful tool for understanding the manner and cause of death in unexpected patient death. The information about the opinions of physicians and risk managers in Japan regarding autopsy is limited. OBJECTIVE: To describe and evaluate the opinions of physicians and risk managers at Japanese teaching hospitals regarding forensic autopsy. DESIGN, SETTING AND PARTICIPANTS: Cross-sectional study of all residency programme directors and risk managers completing a survey in January 2009. Specific clinical scenarios where autopsy would be essential to determine whether medical error occurred and whether medical care contributed to the death of the patient were presented. Respondents gave their opinion regarding the necessity of autopsy and their beliefs about if they would actually recommend it. RESULTS: Of 1113 eligible physicians and 1113 eligible chief risk management officers, 466 physicians (41.9%) and 599 risk managers (53.8%) responded. The majority of physicians and risk managers reported they would recommend an autopsy in cases of unclear medical error or unclear cause and effect relationship of medical care and patient death; however, 10% or more of physicians and 25% or more of risk managers (depending on the situation) reported that they would not recommend an autopsy. Risk managers were less likely than physicians to recommend and believe that autopsy was necessary. CONCLUSIONS: The majority of physicians and risk managers in Japan would recommend autopsy and believe in its necessity in cases of unexpected patient death.

The use of experts in medical malpractice litigation in Japan.

In medical malpractice litigation, the cooperation of medical experts is important. However, the appointment of experts has become problematic in Japan, apparently because many medical experts refuse to act in this capacity. However, this supposition has not until now been supported by quantitative evidence, since the fact that so few judgments in Japan are published made it impossible to investigate the situation. Therefore, we aim to show the state of the use of experts in medical malpractice litigation using objective data. Over the last ten years, the rate of the use of experts has averaged only 22.5%, varying according to region. Experts were used in 24.5% of cases involving an attorney on the patient's side, and in only 3.4% of cases where no attorney was used. The success rate of patients was higher when experts were adopted (39.1%) than when they were not (29.9%). The length of litigation involving experts was 4.0 years, and 2.7 years when no expert was involved. This research suggested the necessity of establishing a formal cooperation system as soon as possible in Japan with no regional maldistribution.

Why are autopsy rates low in Japan? Views of ordinary citizens and doctors in the case of unexpected patient death and medical error.

This article examines what could account for the low autopsy rate in Japan based on the findings from an anonymous, self-administered, structured questionnaire that was given to a sample population of the general public and physicians in Japan. The general public and physicians indicated that autopsy may not be carried out because: (1) conducting an autopsy might result in the accusation that patient death was caused by a medical error even when there was no error (50.4% vs. 13.1%, respectively), (2) suggesting an autopsy makes the families suspicious of a medical error even when there was none (61.0% vs. 19.1%, respectively), (3) families do not want the body to be damaged by autopsy (81.6% vs. 87.3%, respectively), and (4) families do not want to make the patient suffer any more in addition to what he/she has already endured (61.8% vs. 87.1%, respectively).

Patient safety education at Japanese medical schools: results of a nationwide survey.

BACKGROUND: Patient safety education, including error prevention strategies and management of adverse events, has become a topic of worldwide concern. The importance of the patient safety is also recognized in Japan following two serious medical accidents in 1999. Furthermore, educational curriculum guideline revisions in 2008 by relevant the Ministry of Education includes patient safety as part of the core medical curriculum. However, little is known about the patient safety education in Japanese medical schools partly because a comprehensive study has not yet been conducted in this field. Therefore, we have conducted a nationwide survey in order to clarify the current status of patient safety education at medical schools in Japan. RESULTS: Response rate was 60.0% (n = 48/80). Ninety-eight-percent of respondents (n = 47/48) reported integration of patient safety education into their curricula. Thirty-nine percent reported devoting less than five hours to the topic. All schools that teach patient safety reported use of lecture based teaching methods while few used alternative methods, such as role-playing or in-hospital training. Topics related to medical error theory and legal ramifications of error are widely taught while practical topics related to error analysis such as root cause analysis are less often covered. CONCLUSIONS: Based on responses to our survey, most Japanese medical schools have incorporated the topic of patient safety into their curricula. However, the number of hours devoted to the patient safety education is far from the sufficient level with forty percent of medical schools that devote five hours or less to it. In addition, most medical schools employ only the lecture based learning, lacking diversity in teaching methods. Although most medical schools cover basic error theory, error analysis is taught at fewer schools. We still need to make improvements to our medical safety curricula. We believe that this study has the implications for the rest of the world as a model of what is possible and a sounding board for what topics might be important.

Patient safety education at Japanese nursing schools: results of a nationwide survey.

BACKGROUND: Patient safety education is becoming of worldwide interest and concern in the field of healthcare, particularly in the field of nursing. However, as elsewhere, little is known about the extent to which nursing schools have adopted patient safety education into their curricula. We conducted a nationwide survey to characterize patient safety education at nursing schools in Japan. RESULTS: Response rate was 43% overall. Ninety percent of nursing schools have integrated the topic of patient safety education into their curricula. However, 30% reported devoting less than five hours to the topic. All schools use lecture based teaching methods while few used others, such as role playing. Topics related to medical error theory are widely taught, e.g. human factors and theories & models (Swiss Cheese Model, Heinrich's Law) while relatively few schools cover practical topics related to error analysis such as root cause analysis. CONCLUSIONS: Most nursing schools in Japan cover the topic of patient safety, but the number of hours devoted is modest and teaching methods are suboptimal. Even so, national inclusion of patient safety education is a worthy, achievable goal.

Attitudes regarding reporting healthcare-associated patient deaths to the police: A nationwide survey of physicians and RMs in Japanese teaching hospitals.

In Japan, healthcare professionals are required by Article 21 of the Medical Practitioner's Law to report "unnatural deaths" to the police in cases of healthcare-associated patient death. The attitudes of medical personnel at the forefront of clinical medicine regarding reporting have not been described. We investigate the attitudes of physicians and risk managers (RMs) regarding reporting to the police under different circumstances. We sent standardized questionnaires to all hospitals in Japan that participate in the National General Residency Program. We asked physicians and RMs to indicate if they would report to the police or not under scenarios including cases where medical error is present, uncertain, or absent. We also asked if they would report when medical error had occurred and the cause-of-death was directly related, possibly related, or unrelated. We found most physicians believe they would report to the police if medical error clearly caused patient death. We found most RMs believe they would advise physicians to report given the same situation. Less but still a large number of participants favor reporting even when cause-of-death is not clearly related to medical care provided. This tendency persisted even when given a scenario where the hospital director opposed the decision to report.

The acceptability of the decision to withdraw life-sustaining treatment based on the living will and substituted judgements involving decision--the tendency of judiciary decisions and guidelines in Japan.

Recently in Japan, the topic of withdrawing life support is becoming increasingly urgent. The issue of living wills and surrogate decision makers in this process has received little attention. The purpose of this study is to examine recent judiciary decisions in Japan (criminal judgements) and recent guidelines regarding the decision to withdraw life-sustaining treatment based on the living will or surrogate decisions by the patient's family members. We found that most court rulings and all guidelines support withdrawal of life support based on patient wishes stated in a living will. On the other hand, only one judiciary decision supports the use of surrogate wishes in the decision to withdraw support, and the issue of surrogates was not clearly addressed in recent guidelines.

A template for informed consent forms in medical examination and treatment: an intervention study.

BACKGROUND: There are few studies to use a template to ensure that information provided to the patient in the process of informed consent is consistent. To examine the differences between informed consent forms based on a template and those not based on a template. MATERIAL/METHODS: An intervention study using a template for informed consent forms that could be modified according to test/treatment, specialty, setting and patient. Our sample included 22 departments at the University of Tokyo Hospital, a 1100-bed care referral center. Twelve items in each informed consent form were scored. Items included diagnosis and current condition, purpose of procedure, details and nature of procedure, effectiveness, patient specific information, changing one's mind, and the use of illustrations and figures. The 36 possible points for each form were summed for a total possible score of 108 points. Total scores and scores for each item were then compared between pre- and post-test forms. RESULTS: Total number of points significantly increased from 70.9 to 96.9 between pre- and post intervention (p<0.001, paired t test). Internal medicine (pre: 68.6 to post: 101.9) showed a more significant increase in score than surgery (71.9 to 95.2) (ANOVA, pre-post: F(1,106)=324.8 p<0.001; interaction: F(1,106)=11.2, p<0.01). There was no difference in the rate of improvement between treatment and examination forms (ANOVA, pre-post: F(1, 106)=253.3, p<0.001; interaction: F(1,106)=2.8, p=0.1). CONCLUSIONS: A template can increase the number of items described and the thoroughness in which they are described.