Automatic cochlear multimodal 3D image segmentation and analysis using atlas-model-based method.

Objectives: To propose an automated fast cochlear segmentation, length, and volume estimation method from clinical 3D multimodal images which has a potential role in the choice of cochlear implant type, surgery planning, and robotic surgeries.Methods: Two datasets from different countries were used. These datasets include 219 clinical 3D images of cochlea from 3 modalities: CT, CBCT, and MR. The datasets include different ages, genders, and types of cochlear implants. We propose an atlas-model-based method for cochlear segmentation and measurement based on high-resolution µCT model and A-value. The method was evaluated using 3D landmarks located by two experts.Results: The average error was 0.61±0.22 mm and the average time required to process an image was 5.21±0.93 seconds (P<0.001). The volume of the cochlea ranged from 73.96 mm3 to 106.97 mm3, the cochlear length ranged from 36.69 to 45.91 mm at the lateral wall and from 29.12 to 39.05 mm at the organ of Corti.Discussion: We propose a method that produces nine different automated measurements of the cochlea: volume of scala tympani, volume of scala vestibuli, central lengths of the two scalae, the scala tympani lateral wall length, and the organ of Corti length in addition to three measurements related to A-value.Conclusion: This automatic cochlear image segmentation and analysis method can help clinician process multimodal cochlear images in approximately 5 seconds using a simple computer. The proposed method is publicly available for free download as an extension for 3D Slicer software.

Effective optimization strategy for large optimization volume object, remaining volume at risk (RVR):α-value selection and usage from generalized equivalent uniform dose (gEUD) curve deviation perspective.

Objective.A large optimization volume for intensity-modulated radiation therapy (IMRT), such as the remaining volume at risk (RVR), is traditionally unsuitable for dose-volume constraint control and requires planner-specific empirical considerations owing to the patient-specific shape. To enable less empirical optimization, the generalized equivalent uniform dose (gEUD) optimization is effective; however, the utilization of parametera-values remains elusive. Our study clarifies thea-value characteristics for optimization and to enable effectivea-value use.Approach.The gEUD can be obtained as a function of itsa-value, which is the weighted generalized mean; its curve has a continuous, differentiable, and sigmoid shape, deforming in its optimization state with retained curve characteristics. Using differential geometry, the gEUD curve changes in optimization is considered a geodesic deviation intervened by the forces between deforming and retaining the curve. The curvature and gradient of the curve are radically related to optimization. The vertex point (a=ak) was set and thea-value roles were classified into the following three parts of the curve with respect to thea-value: (i) high gradient and middle curvature, (ii) middle gradient and high curvature, and (iii) low gradient and low curvature. Then, a strategy for multiplea-values was then identified using RVR optimization.Main results.Eleven head and neck patients who underwent static seven-field IMRT were used to verify thea-value characteristics and curvature effect for optimization. The lowera-value (i) (a= 1-3) optimization was effective for the whole dose-volume range; in contrast, the effect of highera-value (iii) (a= 12-20) optimization addressed strongly the high-dose range of the dose volume. The middlea-value (ii) (arounda=ak) showed intermediate but effective high-to-low dose reduction. Thesea-value characteristics were observed as superimpositions in the optimization. Thus, multiple gEUD-based optimization was significantly superior to the exponential constraints normally applied to the RVR that surrounds the PTV, normal tissue objective (NTO), resulting in up to 25.9% and 8.1% improvement in dose-volume indices D2% and V10Gy, respectively.Significance.This study revealed an appropriatea-value for gEUD optimization, leading to favorable dose-volume optimization for the RVR region using fixed multiplea-value conditions, despite the very large and patient-specific shape of the region.

Spectroscopic and Density Functional Studies on the Interaction of a Naphthalene Derivative with Anions.

This article highlights the investigation of anion interactions and recognition abilities of naphthalene derivative, [(E)-1-(((4-nitrophenyl)imino)methyl)naphthalen-2-ol], (NIMO) by UV-visible spectroscopically and colorimetrically. NIMO shows selective recognition of F- ions colorimetrically, and a visual color change from yellow to pink is observed by the naked eye. The F- ions recognition is fully reversible in the presence of HSO4- ions. The limit of F- ions detection by NIMO could be possible down to 0.033 ppm-level. A paper strips-based test kit has been demonstrated to detect F- ions selectively by the naked eye, and a smartphone-based method for real sample analysis in the non-aqueous medium has also been demostrated. Spectroscopic behavior is well supported by pKa value calculation and DFT analysis, to find a correlation with receptor analyte interaction. The optical response of NIMO towards the accumulation of F- ions and, subsequently, HSO4- ions as chemical inputs provides an opportunity to construct INH and IMP molecular logic gates.

Interobserver variability of cochlear duct measurements in pediatric cochlear implant candidates.

PURPOSE: The objective of the study was to evaluate the proposed cochlear duct length estimation based on the cochlear 'A value'. Furthermore, we assessed the interobserver variability between radiology and otolaryngology attending physicians and otolaryngology trainees. METHODS: Thirteen pediatric cochlear implant candidates were retrospectively analyzed by three otolaryngology physicians (attending physician, second year, and fourth year trainees) and a radiology attending. The cochlear duct length was calculated based on the formula of Grover et al. The differences in acquired measurements between observers were compared using the Wilcoxon matched signed-rank test. RESULTS: The differences in measurements between the attending otolaryngologist and radiologist were not statistically different, while several significant differences were observed with regard to measurements of attending doctors compared to both residents. In particular, a significant difference between the second year otolaryngology resident and otolaryngology and radiology attending was observed for one side (right ear p = 0.034 and p = 0.012, respectively). Moreover, the fourth year resident calculated significantly different cochlear duct measurements when compared to the attending otolaryngologist (left ear p = 0.014) and radiologist (right ear p = 0.047). Interestingly, differently experienced otolaryngology residents provided significantly different measurements for both ears. CONCLUSIONS: Based on these results, cochlear duct length measurement according to the proposed method may be a reliable and cost-effective method. Indeed, otolaryngology training may be sufficient to provide measurements comparable to radiologists. On the other hand, additional efforts should be invested during otolaryngology training in terms of the evaluation of radiological imaging which may increase the capabilities of otolaryngology residents in this regard.

Shared auditors, information asymmetry degree, and mergers and acquisitions value creation.

The social network is an important factor that affects the value creation of mergers and acquisitions (M&A). The M&A events of China's Listed Companies in 2011-2018 were used as research samples, and this study used the ordinary least square method to test the value creation effect of shared auditors. First, it analyzed the impact of shared auditors on the current, short-term, and long-term M&A value creation. Second, it analyzed the moderating effect of information asymmetry degree. The research results show that shared auditors can increase the enterprise value of both sides of M&A. In addition, related M&A and industry attributes can moderate the relationship between shared auditors and M&A value creation. When the M&A are unrelated and in different industries, shared auditors play a more significant role in the value creation of M&A that have more asymmetric information.

Cochlear base length as predictor for angular insertion depth in incomplete partition type 2 malformations.

INTRODUCTION: The preoperative determination of suitable electrode array lengths for cochlear implantation in inner ear malformations is a matter of debate. The choice is usually based on individual experience and the use of intraoperative probe electrodes. The purpose of this case series was to evaluate the applicability and precision of an angular insertion depth (AID) prediction method, based on a single measurement of the cochlear base length (CBL). METHODS: We retrospectively measured the CBL in preoperative computed tomography (CT) images in 10 ears (8 patients) with incomplete partition type 2 malformation. With the known electrode length (linear insertion depth, LID) the AID at full insertion was retrospectively predicted for each ear with a heuristic equation derived from non-malformed cochleae. Using the intra- or post-implantation cone beam CT images, the actual AID was assessed and compared. The deviations of the predicted from the actual insertion angles were quantified (clinical prediction error) to assess the precision of this single-measure estimation. RESULTS: Electrode arrays with 15 mm (n = 3), 19 mm (n = 2), 24 mm (n = 3), and 26 mm (n = 2) length were implanted. Postoperative AIDs ranged from 211° to 625°. Clinical AID prediction errors from -64° to 62° were observed with a mean of 0° (SD of 44°). In two ears with partial insertion of the electrode, the predicted AID was overestimated. The probe electrode was intraoperatively used in 9/10 cases. CONCLUSION: The analyzed method provides good predictions of the AID based on LID and CBL. It does not account for incomplete insertions, which lead to an overestimation of the AID. The probe electrode is useful and well established in clinical practice. The investigated method could be used for patient-specific electrode length selection in future patients.

Development of liquid chromatographic and UV-visible spectrophotometric methods for determination of pKa values of folic acid antimetabolites.

In this study, the values of ionization/protonation constants (pKa) of pemetrexed and raltitrexed, which are folic acid antimetabolites, were determined by reversed-phase liquid chromatography (RPLC) and UV-visible spectrophotometric methods at 25 °C. The pKass values were evaluated by retention time (tR) in binary acetonitrile-water mixtures with acetonitrile (ACN) contents of 13%, 15%, 17% and 20% (v/v) for the RPLC method and 13%, 15% and 17% (v/v) for the spectrophotometric method. The aqueous pKa values (pKaww) of the studied compounds were calculated from the pKass value using the macroscopic parameters (mole fraction and dielectric constant), which play an important role in solvent properties. In addition, the degree of ionization of pemetrexed and raltitrexed was calculated using the pKaww values.

Molecular interactions in remdesivir-cyclodextrin systems.

Remdesivir (REM) is the first antiviral drug (Veklury™) approved by the Food and Drug Administration for the therapy of COVID-19. Due to its poor water solubility, the preparation of Veklury™ requires a suitable solubilizing excipient at pH 2 conditions. For this purpose, the final formulation contains the randomly substituted sulfobutylether-ß-cyclodextrin (SBEßCD) as a complexing agent. Herein, extensive NMR spectroscopic study with various cyclodextrin (CD) derivatives were conducted to understand the interactions in SBEßCD - REM systems at the molecular level. The pKa value of REM has been determined experimentally for the first time, as the protonation state of the aminopyrrolo-triazine moiety can play a key role in CD-REM inclusion complex formation as SBEßCD has permanent negative charges. The UV-pH titration experiments yielded a pKa of 3.56, thus the majority of REM bears a positive charge at pH 2.0. NMR experiments were performed on ß- and γCD derivatives to determine complex stabilities, stoichiometries and structures. The stability constants were determined by nonlinear curve fitting based on 1H NMR titrations at pH 2.0, while Job's method was used to determine the stoichiometries. ßCD complexes were one order of magnitude more stable than their γCD counterparts. Sulfobutylation resulted in a significant increase in stability and the single isomer derivatives showed unexpectedly high stability values (logK = 4.35 for REM - per-6-SBEßCD). In the case of ßCDs, the ethylbutyl-moiety plays a key role in complexation immersing into the ßCD cavity, while the phenoxy-moiety overtakes and drives the inclusion of REM in the case of γCDs. This is the first comprehensive study of REM-CD complexation, allowing the design of new CD derivatives with tailored stabilities, thereby aiding the formulation or production and even the analytical characterization of REM.

Determination of Cochlear Duct Length With 3D Versus Two-dimensional Methods: A Retrospective Clinical Study of Imaging by Computed Tomography and Cone Beam Computed Tomography.

BACKGROUND: The aim of this study was to compare three different methods for measurement of cochlear duct length (CDL) in the clinical setting for two different imaging modalities, namely computed tomography (CT) and cone-beam computed tomography (CBCT). PATIENTS AND METHODS: One hundred temporal bone data sets (CT: n=50; CBCT: n=50) of non-malformed cochleae were retrospectively analyzed using three different CDL estimation techniques: 3D curved multiplanar reconstruction (cMPR), 2D cMPR and the A-value formula. RESULTS: The data sets belonged to 60 patients (34 males, 26 females; mean age=50.28±18.58 years). For both imaging modalities, application of the 3D cMPR estimation technique led to significantly greater mean CDL values than the two-dimensional methods (p<0.0083). The CDL measurements viewed in CT imaging software were significantly shorter than the corresponding CBCT measurements (p<0.05). Using a linear mixed model, differences in CDL by sex (p=0.796), age (p=0.377) and side of ear (p=0.690) were not significant. CONCLUSION: The 3D cMPR technique was found to provide the most accurate in vivo CDL measurement in non-malformed cochlea in both CT and CBCT imaging compared to 2D methods. The study results also suggest that the higher spatial resolution in CBCT imaging results in more precise CDL determination than in CT.

Structural aspects of 4-aminoquinolines as reversible inhibitors of human acetylcholinesterase and butyrylcholinesterase.

Eight derivatives of 4-aminoquinolines differing in the substituents attached to the C(4)-amino group and C(7) were synthesised and tested as inhibitors of human acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). Both enzymes were inhibited by all of the compounds with inhibition constants (Ki) ranging from 0.50 to 50 µM exhibiting slight selectivity toward AChE over BChE. The most potent inhibitors of AChE were compounds with an n-octylamino chain or adamantyl group. The shortening of the chain length resulted in a decrease in AChE inhibition by 5-20 times. Docking studies revealed that the quinoline group within the AChE active site was positioned in the choline binding site, while the C(4)-amino group substituents, depending on their lipophilicity, could establish hydrogen bonds or π-interactions with residues of the peripheral anionic site. The most potent inhibitors of BChE were compounds with the most voluminous substituent on C(4)-amino group (adamantyl) or those with a stronger electron withdrawing substituent on C(7) (trifluormethyl group). Based on AChE inhibition, compounds with an n-octylamino chain or adamantyl substituent were shown to possess the capacity for further development as potential drugs for treatment of neurodegenerative diseases.

The extent of workaholism in a group of polish nurses.

OBJECTIVE: This study aimed to assess the prevalence of workaholism among Polish nurses. Changes in the work process in Poland have resulted in the expectation of excessive work commitment from employees. Unfortunately, such expectations can contribute to workaholism. The study involved 975 economically active Polish nurses. METHOD: The study was conducted by means of a diagnostic survey, in which we used a standardized questionnaire-the Multidimensional Workaholism Assessment Questionnaire by Malwina Szpitalak. RESULTS: The data obtained show that there is a high risk of workaholism in the study group; almost 6% of all respondents are affected by workaholism, and 40% of all respondents may develop it. The risk is related to the age, seniority, and education level of the nurses. CONCLUSIONS: As there is a high risk of the respondents developing workaholism, it seems advisable to take actions directed at the study group to make them aware of how important it is to maintain a balance between their professional and private lives.

Analyzing the similarity of samples and genes by MG-PCC algorithm, t-SNE-SS and t-SNE-SG maps.

BACKGROUND: For analyzing these gene expression data sets under different samples, clustering and visualizing samples and genes are important methods. However, it is difficult to integrate clustering and visualizing techniques when the similarities of samples and genes are defined by PCC(Person correlation coefficient) measure. RESULTS: Here, for rare samples of gene expression data sets, we use MG-PCC (mini-groups that are defined by PCC) algorithm to divide them into mini-groups, and use t-SNE-SSP maps to display these mini-groups, where the idea of MG-PCC algorithm is that the nearest neighbors should be in the same mini-groups, t-SNE-SSP map is selected from a series of t-SNE(t-statistic Stochastic Neighbor Embedding) maps of standardized samples, and these t-SNE maps have different perplexity parameter. Moreover, for PCC clusters of mass genes, they are displayed by t-SNE-SGI map, where t-SNE-SGI map is selected from a series of t-SNE maps of standardized genes, and these t-SNE maps have different initialization dimensions. Here, t-SNE-SSP and t-SNE-SGI maps are selected by A-value, where A-value is modeled from areas of clustering projections, and t-SNE-SSP and t-SNE-SGI maps are such t-SNE map that has the smallest A-value. CONCLUSIONS: From the analysis of cancer gene expression data sets, we demonstrate that MG-PCC algorithm is able to put tumor and normal samples into their respective mini-groups, and t-SNE-SSP(or t-SNE-SGI) maps are able to display the relationships between mini-groups(or PCC clusters) clearly. Furthermore, t-SNE-SS(m)(or t-SNE-SG(n)) maps are able to construct independent tree diagrams of the nearest sample(or gene) neighbors, where each tree diagram is corresponding to a mini-group of samples(or genes).

Quantum-chemical simulations of the hydration of Pb(II) ion: structure, hydration energies, and pKa1 value.

Thermodynamic and structural aspects of the hydration of Pb(II) ions were explored based on DFT calculations combined with the supermolecular/continuum solvent model. Hydration of Pb(II) was considered as the formation of Pb(H2O)n2+ aqua complexes (n=6-9) from the gas phase Pb(II) ion. Hexa- and hepta-aqua Pb(II) complexes were shown to exhibit the hemidirected symmetry, while those containing eight and nine water molecules are characterized by the holodirected symmetry. The calculations showed that because Pb(H2O)n2+ complexes with six to nine water molecules have comparable thermodynamic stabilities, such complexes are likely to coexist in aqueous solutions. The deprotonation of Pb(H2O)n2+ complexes was shown to result in the formation of the mono-hydroxo complex [Pb(H2O)4OH]+. The pKa1 value determined for this reaction (7.58 for Pb(H2O)62+) was close to the experimental value of 7.61 used in recent models of aquatic equilibria. The density functional method ω-B97X(PCM-UAO) in combination with the atomic basis set 6-311++G(d,p) for O and H and the small-core electron effective pseudopotential (ECP) with the aug-cc-pvdz-PP basis set for Pb can be recommended for such calculations. Graphical abstract Structures of Pb(II) ions with varying numbers of water molecules in the inner hydration shell.

Cochlear helix and duct length identification - Evaluation of different curve fitting techniques.

OBJECTIVE: Within the field of cochlear implantation (CIs), the role of utilizing patient-specific cochlear anatomy for choosing the optimal implant electrode is becoming increasingly important. Unfortunately, performing detailed anatomical measurements of a cochlea using clinical imaging data is rather time consuming and hence difficult to implement into the clinical routine. In order to accelerate clinical cochlear anatomy evaluations, previously developed mathematical models can be adjusted to the patient-specific anatomy by measuring just a few overall cochlear dimensions. However, the accuracy of model-based cochlear anatomy estimations is unclear, and incorrect evaluations may lead to false conclusions regarding the suitability of specific implant electrodes. METHODS: Based on 10 cochleae, an error evaluation of various commonly used curve fitting approaches for cochlear shape and duct length approximation was conducted. Spline tracings of the cochlear contours were used as reference values for the various approximations. RESULTS: Parameterized average cochlear helix models and two of five analytical approaches were found to be suitable for reconstructing the cochlear helical shape and estimating its length. DISCUSSION: Spline curve reconstructions are the most accurate and reliable method for assessing patient-specific cochlear geometry, especially in the case of anatomical irregularities. The most accurate results within the group of model-based evaluations still resulted in mean overall cochlear length deviations of approximately 5%. CONCLUSION: Spline curve reconstructions appear to be the best option for anatomical diagnostics in clinical practice. Retrospective studies can be performed to further evaluate model-based evaluations.

An automated A-value measurement tool for accurate cochlear duct length estimation.

BACKGROUND: There has been renewed interest in the cochlear duct length (CDL) for preoperative cochlear implant electrode selection and postoperative generation of patient-specific frequency maps. The CDL can be estimated by measuring the A-value, which is defined as the length between the round window and the furthest point on the basal turn. Unfortunately, there is significant intra- and inter-observer variability when these measurements are made clinically. The objective of this study was to develop an automated A-value measurement algorithm to improve accuracy and eliminate observer variability. METHOD: Clinical and micro-CT images of 20 cadaveric cochleae specimens were acquired. The micro-CT of one sample was chosen as the atlas, and A-value fiducials were placed onto that image. Image registration (rigid affine and non-rigid B-spline) was applied between the atlas and the 19 remaining clinical CT images. The registration transform was applied to the A-value fiducials, and the A-value was then automatically calculated for each specimen. High resolution micro-CT images of the same 19 specimens were used to measure the gold standard A-values for comparison against the manual and automated methods. RESULTS: The registration algorithm had excellent qualitative overlap between the atlas and target images. The automated method eliminated the observer variability and the systematic underestimation by experts. Manual measurement of the A-value on clinical CT had a mean error of 9.5 ± 4.3% compared to micro-CT, and this improved to an error of 2.7 ± 2.1% using the automated algorithm. Both the automated and manual methods correlated significantly with the gold standard micro-CT A-values (r = 0.70, p < 0.01 and r = 0.69, p < 0.01, respectively). CONCLUSION: An automated A-value measurement tool using atlas-based registration methods was successfully developed and validated. The automated method eliminated the observer variability and improved accuracy as compared to manual measurements by experts. This open-source tool has the potential to benefit cochlear implant recipients in the future.

Measurement of cochlear length using the 'A' value for cochlea basal diameter: A feasibility study.

OBJECTIVES: To determine whether the cochlea basal diameter (A value) measurement can be consistently and precisely obtained from high-resolution temporal bone imaging for use in cochlear length estimation. METHODS: A feasibility study at a tertiary referral center was performed using the temporal bone CTs of 40 consecutive patients. The distance from the round window to the lateral wall was measured for each cochlea by two independent reviewers, a neuroradiologist and an otolaryngologist. The interrater reliability was calculated using the intraclass correlation coefficient (ICC) and the Bland-Altman plot. RESULTS: Forty patients (19 males, 21 females) for a total of 80 cochleae were included. Interrater reliability on the same ear had a high level of agreement by both the ICC and the Bland-Altman plot. ICCs were 0.90 (95% CI: 0.82, 0.94) for the left ear and 0.96 (95% CI: 0.92, 0.98) for the right ear. Bland-Altman plot confirmed interrater reliability with all 96% of measurements falling within the 95% limits of agreement. CONCLUSIONS: Measurement between the round window and lateral cochlear wall can be consistently and reliably obtained from high-resolution temporal bone CT scans. Thus, it is feasible to utilize this method to estimate the cochlear length of patients undergoing cochlear implantation.

Spectrophotometric measurement of minimal erythema dose sites after narrowband ultraviolet B phototesting: clinical implication of spetrophotometric values in phototherapy.

BACKGROUND: The spectrophotometer is well known to be a useful tool for estimating the objective minimal erythema dose (MED) during planning of phototherapy protocol. However, only a few spectrophotometric values are used to evaluate the erythema and pigmentation of the MED site during phototesting. OBJECTIVE: To determinea new meaning of the relationships among spectrophotometric values during phototesting. METHODS: Twenty-five patients with psoriasis and 23 patients with vitiligo were selected before undergoing narrowband ultraviolet B phototherapy. We interpreted the gross findings of erythema and measured the L(*)a(*)b(*) values using a spectrophotometer at each phototest spot. We compared MEDs, basic spectrophotometric values (L(*)a(*)b(*)), and b(*)/L(*) values separately according to skin type, and determined the correlation of each spectrophotometric value and the correlation between a(*) and b(*)/L(*) values. RESULTS: Among L(*)a(*)b(*) values, only b(*) values showed a statistically significant difference between the type III and IV groups (p=0.003). There was a positive correlation only between MEDs and b(*) values (p<0.05). The average b(*)/L(*)value in the type IV group was significantly higher than the type III group (p<0.05). CONCLUSION: The higher b(*) values in type IV skin indicates that skin tanning develops more prominently than type III. The correlation between MEDs and b(*) values may signify that the skin pigmentation status is deepened with the higher MEDs. The difference in b(*)/L(*)values between type III and IV skin reflects that the b(*)/L(*)value is thought to be an index of tanning. The a(*) value, known as an index of erythema, does not influence the degree of tanning.

Spectrophotometric Measurement of Minimal Erythema Dose Sites after Narrowband Ultraviolet B Phototesting: Clinical Implication of Spetrophotometric Values in Phototherapy

BACKGROUND: The spectrophotometer is well known to be a useful tool for estimating the objective minimal erythema dose (MED) during planning of phototherapy protocol. However, only a few spectrophotometric values are used to evaluate the erythema and pigmentation of the MED site during phototesting. OBJECTIVE: To determinea new meaning of the relationships among spectrophotometric values during phototesting. METHODS: Twenty-five patients with psoriasis and 23 patients with vitiligo were selected before undergoing narrowband ultraviolet B phototherapy. We interpreted the gross findings of erythema and measured the L*a*b* values using a spectrophotometer at each phototest spot. We compared MEDs, basic spectrophotometric values (L*a*b*), and b*/L* values separately according to skin type, and determined the correlation of each spectrophotometric value and the correlation between a* and b*/L* values. RESULTS: Among L*a*b* values, only b* values showed a statistically significant difference between the type III and IV groups (p=0.003). There was a positive correlation only between MEDs and b* values (p<0.05). The average b*/L*value in the type IV group was significantly higher than the type III group (p<0.05). CONCLUSION: The higher b* values in type IV skin indicates that skin tanning develops more prominently than type III. The correlation between MEDs and b* values may signify that the skin pigmentation status is deepened with the higher MEDs. The difference in b*/L*values between type III and IV skin reflects that the b*/L*value is thought to be an index of tanning. The a* value, known as an index of erythema, does not influence the degree of tanning.

Toward the accurate calculation of pKa values in water and acetonitrile.

We present a simple approach for the calculation of accurate pKa values in water and acetonitrile based on the straightforward calculation of the gas-phase absolute free energies of the acid and conjugate base with use of only a continuum solvation model to obtain the corresponding solution-phase free energies. Most of the error in such an approach arises from inaccurate differential solvation free energies of the acid and conjugate base which is removed in our approach using a correction based on the realization that the gas-phase acidities have only a small systematic error relative to the dominant systematic error in the differential solvation. The methodology is outlined in the context of the calculation of a set of neutral acids with water as the solvent for a reasonably accurate electronic structure level of theory (DFT), basis set, and implicit solvation model. It is then applied to the comparison of results for three different hybrid density functionals to illustrate the insensitivity to the functional. Finally, the approach is applied to the comparison of results for sets of neutral acids and protonated amine cationic acids in both aqueous (water) and nonaqueous (acetonitrile) solvents. The methodology is shown to generally predict the pKa values for all the cases investigated to within 1 pH unit so long as the differential solvation error is larger than the systematic error in the gas-phase acidity calculations. Such an approach is rather general and does not have additional complications that would arise in a cluster-continuum method, thus giving it strength as a simple high-throughput means to calculate absolute pKa values. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems.

Changes of skin complexion after ultraviolet A (UVA) and ultraviolet B (UVB) exposure / 中华皮肤科杂志

Objective To observe the alteration of skin complexion after UVA and UVB exposure.Methods The back skin of ten females with skin type Ⅲ was subjected to single exposure to solar-simulated UVA of double minimal persistent pigment darkening (MPPD) or UVB of double minimal erythema dose (MED). Skin reflectance was assessed with clinical grading, spectcolometer and Mexameter MX 18 before irra-diation, 6 hours, 1, 7 and 14 days after the irradiation. Results After UVB irradiation, a~* value and erythema index (EI) abruptly increased at 6 hours and peaked on day 2; L~* value sharply declined on day 1; ITA° markedly decreased on day 7; melanin index (MI) declined within the first 2 days, but notably increased on day 7. After UVA irradiation, a~* and El value experienced no apparent changes; L~* value obviously declined at 6 hours; ITA° reached its lowest value on day 14; MI increased only on day 1. Conclusions There is a significant difference in the kinetics and extent of skin complexion changes after UVA and UVB irradiation. EI and a~* value are sensitive and accurate indices for evaluating sunburn, and MI and ITA ° for analyzing tanning.