Menstrual and reproductive factors associated with risk of breast cancer among Indian women: a cross sectional study from National Family Health Survey, 2019-21.

BACKGROUND: The breast cancer is common cancer in women globally. The risk of breast cancer is strongly associated with women's menstrual and reproductive factors that have been established in different countries. Therefore present study was aim to explore the association between menstrual and reproductive factors and the risk of breast cancer screening in Indian women. METHODS: The present study data has been used fifth round of the National Family Health Survey (NFHS-V) with 724,115 women in aged 15-49 in 2019-21. The self-reported ever screened of breast cancer for women aged 30-49 was the main outcome variable of the study. Logistic regression models were used to estimate odds ratios and 95% confidence intervals for breast cancer by menstrual and reproductive factors adjusted for potential confounders. RESULTS: Late menarche (OR = 2.20, 95% CI: 1.48-3.28), irregular menstrual cycle (OR = 1.29, 95% CI: 1.08-3.53)), delay age at first birth (OR = 1.93, 95% CI: 1.11-3.04) and contraceptive pill used (OR = 1.11, 95% CI: 0.74-2.10) were significantly associated to increases the uptake of screening breast cancer. While, a higher number of birth (OR = 0.52, 95% CI: 0.10-1.03), and long duration of breast-feeding practice (OR = 0.75, 95% CI: 0.63-0.91) were reduced to participate for screening breast cancer. CONCLUSION: The results of the study confirm the role of menstrual and reproductive factors in breast cancer in Indian women. Therefore, our findings are imperative for developing breast cancer prevention strategies and better preparedness. Creating awareness and providing knowledge on cancer could be key strategies for the reduction of breast cancer in Indian reproductive age group women.

Prevalence and risk factor of diabetes among the elderly people in West Bengal: evidence-based LASI 1st wave.

BACKGROUND: The complication of Diabetes is one of the important health issues among the older adult population in any region. The higher risks of diabetes prevalence among older adult people in the countries was due to social-cultural changes such as increasing urbanization, dietary changes, without physical activity, and unhealthy lifestyle behavior. The present study examines the prevalence and associated risk factors of diabetes among older adults in the state of West Bengal. METHODS: The first wave of the Longitudinal Ageing Study in India 2017-18 was used to achieve the study objectives. Descriptive statistics with multinomial logistic regression models were used to carry out crude and adjusted odds ratios with 95% confidence intervals and examine the associated risk factors of diabetes prevalence among older adults. RESULTS: The findings of the study indicate that the overall prevalence of diabetes among the study participants was found to be 12.4% which was significantly higher in urban areas (19%) compare to rural areas (6%). The socio-economic and bio-demographic factors like educational status, richest background family, marital status, obesity, and family history of diabetes were significantly associated with higher risks of diabetes prevalence among the older adult population in West Bengal. The risks of diabetes in the richest adult people were significantly higher than in the poorest adult people (OR = 2.78; 95% CI: 1.974-3.917). The higher risks of diabetes mellitus among the richest wealthy people are because of lifestyle behavior, smoking, and tobacco consumption respectively. CONCLUSION: The study needs to policy and awareness program to reduce economic inequality and prevention of diabetes care and treatment-seeking behavior, especially for the older adult population in West Bengal.

Are delay ages at marriage increasing? Pre-marital sexual relation among youth people in the place of residence in India.

BACKGROUND: Adolescent sexual and reproductive health is a major public health issue throughout the world. At the same time shifting of marriage are undergoing discernible changes in country like India. This paper attempts to examine the effect of delay age at marriage on the risks of pre-marital sexual intercourse for the youth people in the place of residence. METHODS: Data used in the present study is from various annual publications of Sample Registration System (SRS) and four round of National Family Health Survey, which was conducted in 2015-2016. The Kaplan-Meier life table technique and multivariate regression models are used to examine the premarital sex by the place of residence and marriage cohort. RESULTS: Findings of the study indicate that the reasons underlying delayed marriage differs between blow 21 years age group and 22-30 years age group. Multinomial analysis clearly shows education, wealth quintile and mass media are major controlling factors of delayed age at marriage. Residing in urban adolescent women who belonged to better economic family background and exposed to mass media had a higher probability to experience premarital sexual intercourse than the rural adolescent in delay age group. CONCLUSION: The study concludes that the restorative the empowerment of youth especially for women and health care provider should consider a multidimensional approach for higher education among youth people and safe sexual behaviour in pre-marital sexual intercourse.

Correction: Iridium-mediated C-S bond activation and transformation: organoiridium(III) thioether, thiolato, sulfinato and thiyl radical compounds. Synthesis, mechanistic, spectral, electrochemical and theoretical aspects.

Correction for 'Iridium-mediated C-S bond activation and transformation: organoiridium(III) thioether, thiolato, sulfinato and thiyl radical compounds. Synthesis, mechanistic, spectral, electrochemical and theoretical aspects' by Ujjwal Das et al., Dalton Trans., 2015, 44, 8625-8639, DOI: 10.1039/C5DT00448A.

Semiparametric multiple inflation count model with application to a smoking cessation study.

Count data are observed by practitioners across various fields. Often, a substantially large proportion of one or some values causes extra variation and may lead to a particular case of mixed structured data. In these cases, a standard count model may lead to poor inference of the parameters involved because of its inability to account for extra variation. Furthermore, we hypothesize a possible nonlinear relationship of a continuous covariate with the logarithm of the mean count and with the probability of belonging to an inflated category. We propose a semiparametric multiple inflation Poisson (MIP) model that considers the two nonlinear link functions. We develop a sieve maximum likelihood estimator (sMLE) for the regression parameters of interest. We establish the asymptotic behavior of the sMLE. Simulations are conducted to evaluate the performance of the proposed sieve MIP (sMIP). Then, we illustrate the methodology on data from a smoking cessation study. Finally, some remarks and opportunities for future research conclude the article.

Approximate confidence intervals for the difference in proportions for partially observed binary data.

We consider partially observed binary matched-pair data. We assume that the incomplete subjects are missing at random. Within this missing framework, we propose an EM-algorithm based approach to construct an interval estimator of the proportion difference incorporating all the subjects. In conjunction with our proposed method, we also present two improvements to the interval estimator through some correction factors. The performances of the three competing methods are then evaluated through extensive simulation. Recommendation for the method is given based on the ability to preserve type-I error for various sample sizes. Finally, the methods are illustrated in two real-world data sets. An R-function is developed to implement the three proposed methods.

Procalcitonin and C-Reactive Protein as an Early Predictor of Infection in Elective Gastrointestinal Cancer Surgery-a Prospective Observational Study.

BACKGROUND: Postoperative infections are a common entity following elective gastrointestinal surgery among which intra-abdominal infection is notorious and life threatening. Early detection could reduce postoperative morbidity and permit safe and early discharge. This study was aimed to establish the usefulness of procalcitonin (PCT) and C-reactive protein (CRP) on postoperative day 3 as reliable markers for early detection of intra-abdominal infection and other postoperative infections following elective gastrointestinal cancer surgery. METHODS: A total of 125 patients following elective gastrointestinal cancer surgery were prospectively observed until discharge from January 2018 to December 2019. The incidence of intra-abdominal infections and other postoperative infections was recorded. Serum PCT and CRP were estimated on postoperative day 3 for all the patients. ROC analysis of PCT and CRP was performed to establish their predictability in detecting these infections. Risk factors for postoperative infections were also studied. RESULTS: The incidence of intra-abdominal infection (IAI) was 24%. The difference in PCT between the infected and non-infected patients was statistically significant (p = 0.001) but not in CRP (p = 0.223). On ROC analysis of CRP and PCT in detecting IAI, the areas under the curve were 0.494 and 0.615 respectively. CONCLUSION: Raised serum PCT values on postoperative day 3 indicate the presence of infections and should prompt the surgeon to consider other investigations to confirm the presence of IAI and other postoperative infections and plan early intervention thus expediting the postoperative recovery. CLINICAL TRIAL REGISTRATION NUMBER: CTRI/2018/12/016695.

Pancreaticoduodenectomy: Impact of Volume on Outcomes at a Tertiary Care Center-Our Experience in Single Institute of Nepal.

BACKGROUND: Pancreaticoduodenectomy is a complex high-risk surgical procedure usually done for malignant disease carrying significant postoperative morbidity and mortality. An audit and analysis of rate of postoperative morbidity and mortality and the impact of case volume can provide information about the lacunas in patient care and methods to improve it for safe and early discharge of patients. This study was conducted to find out demographic profile, the rate of perioperative morbidities, mortality, and impact of case volume on patients undergoing pancreaticoduodenectomy for malignant disease which may serve as a guide to uplift the patient care in our center. METHODS: Retrospective analysis of prospectively collected data of patients undergoing pancreaticoduodenectomy from 2015 to 2019 was performed. A total of 62 patients were included in the study. Patient's clinic-demographic details and intraoperative and postoperative events were recorded. The rate of various postoperative morbidities and mortality and year-wise trend of these factors were analyzed. RESULTS: Most of the patients were in the sixth decade of life (38.7%) with male preponderance (61.3%). Pancreatic cancer was most commonly seen followed by cholangiocarcinoma (46.8%). SSI (32.3%), intraabdominal collection (25.8%), anastomotic leak (14.5%), pancreatic fistula (22.6%), and postpancreatectomy hemorrhage (8.1%) were the major postoperative events. Mortality was found in 12.9% patients. CONCLUSION: There has been a decrease in rate of all these postoperative adverse events and improvement in the intraoperative blood loss and surgical duration with advancing years and increasing number of cases.

Effect of Main Versus Ancillary Ligand Substitution on the Photophysical Properties of a Series of Ir(III) Complexes: A Detailed Theoretical Investigation.

Herein, we report the effects of different electron-withdrawing groups (EWG) (-F) and electron-donating groups (EDG) (-OMe and -NH2) on main ligands (ppy) and ancillary (acac) of [Ir(ppy)2(acac)] [ppy = 2-phenylpyridine; acac = acetylacetonato] using seven complexes by DFT and TDDFT calculations. We find that irrespective of the substituents, absorption of ppy-substituted complexes is blue-shifted, while for the acac-substituted complexes, it is red-shifted. The calculations also show that the substitution of EWGs causes an overall drop in the frontier molecular orbital energy levels; however, we observed a reverse effect for EDGs. To calculate the radiative rate kr, we considered the spin-orbit coupling matrix element (SOCME) (⟨T1|HSOC|Sn⟩) between Sn (n = 1, 2, etc.) excited state and T1, transition dipole moment (µ(Sn)), and the energy difference between excited singlet states Sn and T1 state (ΔE(Sn - T1)). To compare the temperature-independent nonradiative process, we considered SOC between T1 and S0 (⟨T1|HSOC|S0⟩) and the energy gap between optimized T1 and S0 states. Furthermore, to formulate the temperature-dependent nonradiative rate, we computed the activation barrier (E1) for the metal-to-ligand state (3MLCT) to a metal-centered state (3MC) conversion. The emission peaks show that the changes of triplet state T1 from 3MLCT → 3MC via transition states (3TS) and 3MLCT → 1GS (GS = ground state) via the 3MC/1GS minimum energy crossing point are not much affected by the nature of substituents in the ancillary and the main ligand. The order of E1 for the investigated complexes indicates that electron-donating substituents -OMe at both ppy and acac ligands can cause a decrease in nonradiative rate constants. Natural transition orbitals of the complexes show that they are mainly localized on the main ligand ppy and the Ir atoms and hardly on the ancillary ligand acac.

The growth of methylammonium lead iodide perovskites by close space vapor transport.

Vapor deposition processes have shown promise for high-quality perovskite solar cells with potential pathways for scale-up to large area manufacturing. Here, we present a sequential close space vapor transport process to deposit CH3NH3PbI3 (MAPI) perovskite thin films by depositing a layer of PbI2 then reacting it with CH3NH3I (MAI) vapor. We find that, at T = 100 °C and pressure = 9 torr, a ∼225 nm-thick PbI2 film requires ≥125 minutes in MAI vapor to form a fully-reacted MAPI film. Raising the temperature to 160 °C increases the rate of reaction, such that MAPI forms within 15 minutes, but with reduced surface coverage. The reaction kinetics can be approximated as roughly first-order with respect to PbI2, though there is evidence for a more complicated functional relation. Perovskite films reacted at 100 °C for 150 minutes were fabricated into solar cells with an SLG/ITO/CdS/MAPI/Spiro-OMeTAD/Au structure, and a device efficiency of 12.1% was achieved. These results validate the close space vapor transport process and serve as an advance toward scaled-up, vapor-phase perovskite manufacturing through continuous vapor transport deposition.

Analysis of interval-censored competing risks data under missing causes.

In this article, interval-censored competing risks data are analyzed when some of the causes of failure are missing. The vertical modeling approach has been proposed here. This approach utilizes the data to extract information to the maximum possible extent especially when some causes of failure are missing. The maximum likelihood estimates of the model parameters are obtained. The asymptotic confidence intervals for the model parameters are constructed using approaches based on observed Fisher information matrix, and parametric bootstrap. A simulation study is considered in detail to assess the performance of the point and interval estimators. It is observed that the proposed analysis performs better than the complete case analysis. This establishes the fact that the our methodology is an extremely useful technique for interval-censored competing risks data when some of the causes of failure are missing. Such analysis seems to be quite useful for smaller sample sizes where complete case analysis may have a significant impact on the inferential procedures. Through Monte Carlo simulations, the effect of a possible model misspecification is also assessed on the basis of the cumulative incidence function. For illustration purposes, three datasets are analyzed and in all cases the conclusion appears to be quite realistic.

Correlation between in Situ Diagnostics of the Hydrogen Plasma and the Interface Passivation Quality of Hydrogen Plasma Post-Treated a-Si:H in Silicon Heterojunction Solar Cells.

Passivation of the interface defect states is crucial to mitigate the recombination losses in silicon solar cells. In this work, we have investigated the role of hydrogen plasma treatment (HPT) to passivate the interfacial defects between crystalline (c-Si) and hydrogenated amorphous silicon (a-Si:H) in silicon heterojunction (SHJ) solar cells. For the first time, we have found a correlation between the dynamic properties of hydrogen plasma and passivation quality of the films by using in situ optical emission spectroscopy and quasi-steady state photoconductance measurement. The optimum condition for saturation of the dangling bonds by HPT has been studied in detail by tuning the excited hydrogen (H) species and ion bombardment energies by controlling physical parameters like plasma current and chamber pressure. We have investigated the role of annealing after HPT to redistribute the H in the post-treated a-Si:H film and have obtained an i Voc of 755 mV, minority carrier lifetime (τeff) of 4.6 ms, and SRV of 1.5 cm/s on test structures having only an 10 nm intrinsic a-Si:H layer on textured silicon wafers. The H bond configuration at the interface of a-Si:H and c-Si has been investigated by Fourier transform infrared spectroscopy, which demonstrates improved monohydride bonding in the films after HPT derived from the analysis of microstructure parameter and H concentration values. Raman spectroscopy shows the absence of the nanocrystalline fraction after HPT and verifies reduced coordination defects due to annealing after HPT. The proof of concept has been validated by fabricated SHJ solar cells having a Voc of 729 mV and efficiency of 18.7% after HPT, with the best cell efficiency reaching 20.2% after doped layer optimization. The decrease in reverse saturation current and ideality factor after HPT verifies that the improvement in performance is from reduced recombination losses at the interface due to passivation of defects in midgap states.

Surface Defect Passivation and Reaction of c-Si in H2S.

A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H2S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τeff) of >2000 µs corresponding to a surface recombination velocity of <3 cm/s is achieved at a temperature range of 550-650 °C. X-ray photoelectron spectroscopy (XPS) confirmed the bonding states of Si and S and provides insights into the reaction pathway of Si with H2S and other impurity elements both during and after the reaction. Quantitative analysis of XPS spectra showed that the τeff increases with an increase in the surface S content up to ∼3.5% and stabilizes thereafter, indicative of surface passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H2O and O2. This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

APOE-ɛ4 Carrier Status and Donepezil Response in Patients with Alzheimer's Disease.

BACKGROUND: Previous studies have investigated associations between apolipoprotein E (APOE)-ɛ4 allele status and acetylcholinesterase inhibitor treatment response in patients with Alzheimer's disease. The ability to draw definitive conclusions regarding the effect of APOE-ɛ4 genotype on treatment response has been hindered by inconsistent results among studies and methodological limitations that restrict interpretation of study findings. OBJECTIVE: To determine whether APOE-ɛ4 carrier status influences the magnitude of change in 13-item Alzheimer's Disease Assessment Scale-Cognitive Subscale (ADAS-cog) score associated with acetylcholinesterase inhibitor treatment (i.e., donepezil). METHODS: Analyses were performed using pooled data from the donepezil and placebo treatment arms of three consecutive, similarly designed, 12-week, multi-national, randomized clinical studies that enrolled patients with mild-to-moderate Alzheimer's disease. Correlations between APOE-ɛ4 carrier status and ADAS-cog scores were evaluated using analysis of covariance. RESULTS: No appreciable interaction between donepezil response and APOE-ɛ4 carrier status or copy number was detected. Both carriers and non-carriers of APOE-ɛ4 who received donepezil experienced significant improvements from baseline in ADAS-cog score versus placebo (p <  0.05). Change from baseline to final observation in the donepezil treatment group was - 2.95 for APOE-ɛ4 carriers and - 4.09 for non-carriers (p = 0.23). In contrast, non-carriers of APOE-ɛ4 in the placebo treatment group exhibited a greater improvement from baseline versus carriers (-2.38 versus - 0.60, p = 0.05). CONCLUSION: Within this population, APOE genotype had no statistically significant effect on cognitive response to donepezil treatment; however, APOE-ɛ4 allele status was associated with a difference in the magnitude of the change in ADAS-cog of placebo-treated patients.

Iridium-mediated C-S bond activation and transformation: organoiridium(III) thioether, thiolato, sulfinato and thiyl radical compounds. Synthesis, mechanistic, spectral, electrochemical and theoretical aspects.

An attractive methodology, single-electron transfer (SET) reductive cleavage of the C-S bond mediated by a metal in the presence of the external stimuli PPh3, has been applied to the kinetically inert IrCl3 in order to synthesize the thiolato complex [Ir(III)(L(S))Cl(PPh3)2] 3 from precursor thioether complexes [Ir(III)(L(SR))Cl2(PPh3)] (R = alkyl) 2. The aforesaid cleavage process in association with (arene)C-H activation furnishes a new class of organosulfur compounds of iridium(III). The thiolato chelate 3 displays a reversible oxidative wave at 0.75 V vs. Ag/AgCl signifying its remarkable nucleophilic character. The high electron density on the thiolato-S vis-à-vis superior nucleophilicity can be envisaged through the formation of a number of S-centered derivatives. This observation has been corroborated with the nature of HOMO in 3, which assumes 49% of S(3p). Notably, the facile oxidative nature of 3 makes it an apposite precursor for metal-stabilized thiyl radical species. Indeed, iridium(III)-stabilized 3˙(+) can be generated by chemical/electrochemical means. The axial EPR spectra with g ∼ 2.0 along with theoretical analysis of SOMO (S(3p) 24% + Ph(π) 43% + d(yz) 15%) and spin density (ρ(S) = +0.543, ρ(Ph) = +0.315, ρ(Ir) = +0.151) of one-electron oxidized 3˙(+) validate the iridium-stabilized thiyl radical description. This observation suggests that the CNS coordination mode in thiophenolato complex 3 is redox-active. Complex 3 is very prone to S-centered oxidation under normal aerobic conditions to yield metallosulfoxide [Ir(III)(L(SO2))Cl(PPh3)2] 4. The enhanced nucleophilicity of thiolato-S can also be manifested via the smooth S-C bond making process with alkyl halides (R'X, R' = Me and allyl; X = Br, I) and subsequent formation of thioether complexes of type [Ir(III)(L(SR'))ClX(PPh3)] 5. The organosulfur compounds of iridium(III) exhibit rich spectral properties including luminescence and the origin of these transitions is scrutinized with DFT and TD-DFT methods.

Mixed modeling of meta-analysis P-values (MixMAP) suggests multiple novel gene loci for low density lipoprotein cholesterol.

Informing missing heritability for complex disease will likely require leveraging information across multiple SNPs within a gene region simultaneously to characterize gene and locus-level contributions to disease phenotypes. To this aim, we introduce a novel strategy, termed Mixed modeling of Meta-Analysis P-values (MixMAP), that draws on a principled statistical modeling framework and the vast array of summary data now available from genetic association studies, to test formally for locus level association. The primary inputs to this approach are: (a) single SNP level p-values for tests of association; and (b) the mapping of SNPs to genomic regions. The output of MixMAP is comprised of locus level estimates and tests of association. In application of MixMAP to summary data from the Global Lipids Gene Consortium, we suggest twelve new loci (PKN, FN1, UGT1A1, PPARG, DMDGH, PPARD, CDK6, VPS13B, GAD2, GAB2, APOH and NPC1) for low-density lipoprotein cholesterol (LDL-C), a causal risk factor for cardiovascular disease and we also demonstrate the potential utility of MixMAP in small data settings. Overall, MixMAP offers novel and complementary information as compared to SNP-based analysis approaches and is straightforward to implement with existing open-source statistical software tools.

Corrected profile likelihood confidence interval for binomial paired incomplete data.

Clinical trials often use paired binomial data as their clinical endpoint. The confidence interval is frequently used to estimate the treatment performance. Tang et al. (2009) have proposed exact and approximate unconditional methods for constructing a confidence interval in the presence of incomplete paired binary data. The approach proposed by Tang et al. can be overly conservative with large expected confidence interval width (ECIW) in some situations. We propose a profile likelihood-based method with a Jeffreys' prior correction to construct the confidence interval. This approach generates confidence interval with a much better coverage probability and shorter ECIWs. The performances of the method along with the corrections are demonstrated through extensive simulation. Finally, three real world data sets are analyzed by all the methods. Statistical Analysis System (SAS) codes to execute the profile likelihood-based methods are also presented.

InterPro in 2011: new developments in the family and domain prediction database.

InterPro (http://www.ebi.ac.uk/interpro/) is a database that integrates diverse information about protein families, domains and functional sites, and makes it freely available to the public via Web-based interfaces and services. Central to the database are diagnostic models, known as signatures, against which protein sequences can be searched to determine their potential function. InterPro has utility in the large-scale analysis of whole genomes and meta-genomes, as well as in characterizing individual protein sequences. Herein we give an overview of new developments in the database and its associated software since 2009, including updates to database content, curation processes and Web and programmatic interfaces.

InterPro: the integrative protein signature database.

The InterPro database (http://www.ebi.ac.uk/interpro/) integrates together predictive models or 'signatures' representing protein domains, families and functional sites from multiple, diverse source databases: Gene3D, PANTHER, Pfam, PIRSF, PRINTS, ProDom, PROSITE, SMART, SUPERFAMILY and TIGRFAMs. Integration is performed manually and approximately half of the total approximately 58,000 signatures available in the source databases belong to an InterPro entry. Recently, we have started to also display the remaining un-integrated signatures via our web interface. Other developments include the provision of non-signature data, such as structural data, in new XML files on our FTP site, as well as the inclusion of matchless UniProtKB proteins in the existing match XML files. The web interface has been extended and now links out to the ADAN predicted protein-protein interaction database and the SPICE and Dasty viewers. The latest public release (v18.0) covers 79.8% of UniProtKB (v14.1) and consists of 16 549 entries. InterPro data may be accessed either via the web address above, via web services, by downloading files by anonymous FTP or by using the InterProScan search software (http://www.ebi.ac.uk/Tools/InterProScan/).

RhCl3-assisted C-H and C-S bond scissions: isomeric self-association of organorhodium(iii) thiolato complex. synthesis, structure, and electrochemistry.

The ligating properties of alkyl 2-(phenylazo)phenyl thioether 1 (HL(R); R = Me, CH(2)Ph) toward Rh(III) have been examined. A novel hexacoordinated orthometalated rhodium(III) thiolato complex trans-[Rh(L)Cl(PPh3)2] 5 has been synthesized from 1 and RhCl(3).3H(2)O in the presence of excess PPh(3) via in situ C(sp(2))-H and C(sp(3))-S bond scissions, which is the first example for a coordination compound of [L](2-). We were also able to isolate the intermediate organothioether rhodium(III) compound trans-[Rh(L(R))Cl(2)(PPh(3))] 6 with 1 equiv of PPh(3) relative to both 1 and RhCl(3).3H2O in the course of the synthesis of the S-dealkylated product. PPh(3) plays a crucial role in the C(sp(3))-S cleavage process. A plausible mechanistic pathway is presented for C-S bond cleavage, and reductive cleavage by single-electron transfer mechanism is likely to be operative. The electronically and coordinatively saturated thiolato complex 5, indefinitely stable in the solid state, undergoes spontaneous self-dimerization in solution via dissociation of one coordinated PPh3 molecule to afford edge-shared bioctahedral anti-[Rh(L)Cl(PPh(3))]2 7 and syn-[Rh(L)Cl(PPh(3))]2 8 isomers. All the synthesized organosulfur rhodium(III) compounds were isolated as both air- and moisture-stable solids and spectroscopically characterized in both solution and solid states. In addition, all the representative members have been authenticated by single-crystal X-ray structure analyses. Availability of the isomeric dimers provides an opportunity to recognize the presence of noncovalent intramolecular "metallochelate-metallochelate" interaction in the sterically encumbered syn isomer. Unlike other organosulfur rhodium complexes, the monomeric thiolato complex 5 exhibits a fully reversible oxidative wave at 0.82 V vs Ag/AgCl, which is supposed to be primarily centered on the thiolato sulfur atom, and such perception is consistent with the DFT study. Formation of rhodium-bound thiyl radical cation 5(*+) by electrochemical oxidation was scrutinized by EPR spectroscopy.