Discrimination and analytical profiling of colored printed documents using ATR-FTIR spectroscopy coupled with explorative and predictive statistical analysis: Part I.

Printed documents are a common form of evidence in forensic document examination. The integration of spectroscopy with chemometrics have evolved evidential analytical interpretation of printing inks. However, we report the first ever study that explores the examination of both black and colored printed documents combined with explorative Principal Component Analysis (PCA) and supervised techniques viz. Soft independent modelling of class analogy (SIMCA) and Partial Least Square- Discriminant Analysis (PLS-DA). The study investigated 74 (40 Ink-based and 34 Toner- based) colored printed document samples using ATR-FTIR to discriminate and determine the source of origin of an unknown printed document using a non-destructive approach. Qualitative analysis by ATR- FTIR indicated the presence of polystyrene, bisphenol A and acrylates as the common binder polymers in the samples. The study was also able to obtain pigment information like presence of PR 57 and PR 146 in magenta, Carbon black in black, Copper Phthalocyanine and PB 15 in Cyan and PY 74 in yellow colored printed samples. Further, PCA has been used as an explorative technique that showed a variance of 97 % in the dataset and indicating that the color Cyan contributes to the maximum classification accuracy. SIMCA has been used as a supervised method to classify the known and test samples to their respective defined classes. However, SIMCA could only classify Toner-based samples in their respective class and inconclusive results were obtained in case of Ink-based samples. Finally, PLS-DA was also used to classify the two class of samples which resulted in a discrimination accuracy of 98.6 %. The derived model was also used for validation study on blind test samples which provided 100 % classification results.

An Overview of Security Materials in Banknotes and Analytical Techniques in Detecting Counterfeits.

Counterfeiting or forged imitation of banknotes is a perpetual practice engulfing global economies. This not only poses challenges for the material scientists to come forth with advanced security materials but also demands veracious forensic examination to detect counterfeits. The present article pursues novel efforts in summarizing a study that lays focus on the recent optical and analytical examinations being used for the characterization and detection of chemical profiles of authentic and counterfeited banknotes. The article briefs the trends in banknote materials, security paper manufacturing process, security inks used for printing, and types of the security printing process in banknote practices. Reported literature shows the introduction of new anti-counterfeiting materials viz. magnetically-responsive photonic anti-counterfeiting watermarks, and fluorescent nanoparticles that can be used as anti-counterfeiting inks, anti-stokes inks, metameric inks, etc. Analytical techniques such as IR spectroscopy, Raman spectroscopy, Mossbauer spectroscopy, X-ray diffraction, X-ray fluorescence, LIBS, XRF, ELDI-MS, EASI/DESI-MS, HPLC, VSC, AFM, etc. in conjunction with different chemometrics approaches have been critically discussed. The study also presents the future scope in banknote examination like the use of hyper spectral imaging and sensor-based counterfeit detection systems.

Forensic examination of thermal papers using Video Spectral Comparator (VSC) and ATR-FTIR spectroscopy coupled with chemometrics: Non-destructive approach.

Thermal papers are replacing the conventional form of printing and are being extensively used across the globe. This study encompasses a non-destructive approach to examine thermal papers by using ATR-FTIR spectroscopy and Video Spectral Comparator (VSC), where the former technique helps in characterizing and discriminating different samples and the latter helps in deciphering the faded prints on thermal paper. The qualitative analysis of the spectroscopic data based on peak to peak comparison and quantitative analysis using chemometrics has been done to obtain high discriminating power. Multivariate analysis using HCA gave a discriminating power of 83.82% and PCA showed a variance of 95.64%. The strength of the study is portrayed through the decipherment of artificially and naturally faded thermal papers using VSC and analyzing the effect of different storing conditions on their rate of fading.

Wolffian Origin of Vagina Unfolds the Embryopathogenesis of OHVIRA (Obstructed Hemivagina and Ipsilateral Renal Anomaly) Syndrome and Places OHVIRA as a Female Counterpart of Zinner Syndrome in Males.

BACKGROUND: The classical theory of Müllerian origin of upper vagina fails to explain complex urogenital malformations like OHVIRA syndrome; the Acien's hypothesis, however, unravels the hidden embryopathogenesis. As per Acien, Wolffian (mesonephric) ducts instead of Müllerian ducts and sinovaginal bulbs, give rise to the vagina. The new hypothesis, however, retains the concept of origin of the ureters (with ureters inducing renal development) by the former and the uterus by Müllerian ducts. Thus, a failure of development of mesonephros/mesonephric duct gives rise to absent ureters and hence absent homolateral kidney; blind ending (obstructed) ipsilateral hemivagina and cessation of support to paramesonephric ducts which leads to unfused uterus (uterus didelphys). Hence, the new hypothesis explains all components of OHVIRA syndrome. On a parallel track, unilateral anomalous development of the mesonephros in males causes atresia of the homolateral ejaculatory duct that results in obstruction of the proximally placed seminal vesicle. Besides, there is absence of the ipsilateral kidney (Zinner syndrome). CASE REPORT: In this manuscript, we describe four cases of OHVIRA syndrome. Case 1 was a 34-year-old nulligravida, married since fourteen years, who presented with a 5-month history of pelvic inflammatory disease and dyspareunia. Regular menses in the patient and azoospermia in her husband delayed the diagnosis. Case 2 was a 14-year-old girl who presented with dysmenorrhea and lower abdominal pain since a few months. Case 3 was a 27-year-old female who presented with infertility and dysmenorrhea. Case 4 was a 15-year-old female who presented with a one-year history of dysmenorrhea and cyclic pelvic pain. In all cases, one of the uterine horns revealed collection due to a hemivaginal septum and an absent ipsilateral kidney; thus, establishing the diagnosis of OHVIRA syndrome. The case 4 additionally revealed homolateral vaginal agenesis. CONCLUSIONS: On the basis of our 4 cases, we support the Acien's hypothesis of Wolffian origin of vagina which explains the development of OHVIRA syndrome. Besides, we emphasize the need to suspect this syndrome in a female with a pelvic mass and absence of homolateral kidney. Finally, we believe that OHVIRA due to its Wolffian origin is a female equivalent of Zinner syndrome in males. Therefore, we propose OSVIRA (Obstructed Seminal Vesicle and Ipsilateral Renal Agenesis) as an acronym for Zinner syndrome analogous to OHVIRA.

Measurement of total ultrasonic power using thermal expansion and change in buoyancy of an absorbing target.

The Radiation Force Balance (RFB) technique is well established and most widely used for the measurement of total ultrasonic power radiated by ultrasonic transducer. The technique is used as a primary standard for calibration of ultrasonic transducers with relatively fair uncertainty in the low power (below 1 W) regime. In this technique, uncertainty comparatively increases in the range of few watts wherein the effects such as thermal heating of the target, cavitations, and acoustic streaming dominate. In addition, error in the measurement of ultrasonic power is also caused due to movement of absorber at relatively high radiated force which occurs at high power level. In this article a new technique is proposed which does not measure the balance output during transducer energized state as done in RFB. It utilizes the change in buoyancy of the absorbing target due to local thermal heating. The linear thermal expansion of the target changes the apparent mass in water due to buoyancy change. This forms the basis for the measurement of ultrasonic power particularly in watts range. The proposed method comparatively reduces uncertainty caused by various ultrasonic effects that occur at high power such as overshoot due to momentum of target at higher radiated force. The functionality of the technique has been tested and compared with the existing internationally recommended RFB technique.

Primary measurement of total ultrasonic power with improved accuracy in rf voltage measurement.

Out of the various existing ultrasonic power measurement techniques, the radiation force balance method using microbalance is most widely used in low power (below 1 W) regime. The major source of uncertainty associated with this technique is the error in ac voltage measurement applied to the transducer for the generation of ultrasonic waves. The sources that deteriorate the ac voltage measurement accuracy include cable length and impedance mismatch. We introduce a new differential peak to peak measurement approach to reduce the ac voltage measurement error. The method holds the average peak amplitude of each polarity. Ultralow offset difference amplifier is used to measure peak to peak voltage. The method is insensitive to the variations in the dc offset of the source. The functionality of this method has been tested and compared with the conventional rf voltage measurement method. The output of this proposed technique is dc, which can be measured with an error of less than 0.1%.

AOT water-in-oil microemulsions as a penetration enhancer in transdermal drug delivery of 5-fluorouracil.

In vitro transdermal permeation of 5-fluorouracil (antineoplastic), a hydrophilic drug encapsulated in AOT/water/isopropylmyristate water-in-oil microemulsions (MEs), were studied using a modified Keshary and Chien diffusion cell. AOT (aerosol-OT or sodium bis(2-ethylhexyl) sulfosuccinate) is an anionic surfactant, which forms 'water-in-oil' ME in non-aqueous medium. The effect of water and AOT concentrations in MEs to the transdermal permeation of 5-fluorouracil through hairless mouse skin was investigated. MEs with 5:95 weight ratio of AOT:isopropylmyristate, containing 0.9, 1.8, 2.7 and 3.6% w/w of water have showed 1.68-, 2.36-, 3.58- and 3.77-fold increases in the skin flux of 5-fluorouracil (5-FU) respectively, compared to the aqueous solution of drug. The MEs with 5:95, 9:91 and 13:87 weight ratio of AOT:isopropyl myristate at fixed water content W0=15 (W0=[H2O]/AOT]) gave 3.58-, 5.04- and 6.3-fold enhancement of drug. In addition, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy was used to examine the effect of ME on lipid alkyl chain, hydration level, and corneocyte cells of the stratum corneum (SC). Results reveal that the ME interacts with a component of the SC and perturbs its architectural structure. The extent of perturbation in the SC depends on the concentration of water and AOT in the ME. Preliminary dermal toxicity studies indicate that the AOT/water/isopropylmyristate ME be safe for the transdermal permeation of 5-FU.