Indian visceral leishmaniasis with extensive lymphadenopathy - An unusual presentation: A case report with literature review.

Visceral leishmaniasis (VL), also known as kala-azar, is a life-threatening systemic disease caused by the obligate intracellular protozoan, Leishmania, and transmitted to humans by the female phlebotomine sand fly (Phlebotomus argentipes). The disease is fatal, if left untreated. We report a case of a patient clinically suspected of disseminated tuberculosis, but fine needle aspiration cytology of cervical and axillary lymph nodes yielded a diagnosis of leishmaniasis. Diagnosis of VL was challenging as the disease closely mimicked tuberculosis in the setting of extensive lymphadenopathy including conglomerate of mesenteric lymph nodes, on and off fever, and granulomatous lymphadenitis on aspiration. Bone marrow examination was further performed. A detailed workup revealed patient to be severely immunocompromised and newly diagnosed human immunodeficiency virus (HIV) positive. Worldwide, India has the largest number of VL cases, accounting for 40%-50% of world's disease burden and the second largest HIV-infected population, accounting for approximately 10% of the global disease burden. HIV increases the risk of developing VL by 100-2320 times in endemic areas and concurrently VL promotes the clinical progression of HIV disease. Co-infection with HIV alters the body's immune response to leishmaniasis thus leading to unusual presentations. This case highlights the diagnostic problem in the aforesaid setting. Moreover, co-infection with HIV in VL can be a potential source of drug resistance. An early diagnosis and intensified treatment is the key to patient management.

[32]π Fused Core-Modified Heptaphyrin with Möbius Aromaticity.

A new fused core-modified 32π heptaphyrin with Möbius aromatic character is reported. The (1)H NMR data indicated a weak Möbius aromaticity at 298 K; however, at 213-183 K, the molecule predominates [4n]π Möbius conformation with strong diatropic ring current, which was further confirmed by X-ray analysis. The protonation experiment led to preservation of the Möbius aromaticity at 298 K. Nevertheless, the experimental results were further supported by theoretical studies. Overall, this study represents the first example of Möbius aromatic fused core-modified expanded porphyrin.

Pretibial Myxedema Associated with Euthyroid Hashimoto's Thyroiditis: A Case Report.

Pretibial myxedema (PM) is an infiltrative dermopathy which is seen in grave's disease. It is also associated with hypothyroidism, but is infrequently seen in Hashimoto's thyroiditis. Lesions are seen commonly over pretibial region as non-pitting oedema or with a plaque morphology. Heat shock protein (HSP) has been reported to be expressed by fibroblasts present at affected site, which cause lesions of PM. Histopathology differentiates it from other dermatoses. Lesions usually resolve spontaneously, but therapies like potent topical steroids, intralesional steroids, gamma globulin, pentoxifylline, surgery and radiotherapy are indicated. Here, a case of PM with euthyroid Hashimoto's thyroiditis has been reported, which was proven by histopathology.

A Clinical Study of Vitiligo in a Rural Set up of Gujarat.

INTRODUCTION: Vitiligo is an acquired depigmentary condition caused by inactivation or destruction of melanocytes in epidermis and hair follicle. Worldwide incidence of 1% has been reported; similar to various dermatological clinics in India. Widespread prejudice, ignorance, taboos, lack of scientific appraisal, and confusion of vitiligo with leprosy makes it an immense psychological stress. AIM: To know the clinical profile of vitiligo patient with associated cofactors. MATERIALS AND METHODS: Total 1,010 patients of vitiligo attended in outpatient department at Shree Krishna Hospital (SKH) and Matar camp, Gujarat over 1 year period from August 2011 to July 2012 were included in this study. Detail history and clinical examination of patients were done. RESULTS: Out of 1,010 patients 57.3% were females and 42.7 % were males. Most cases developed vitiligo by 2(nd) decade of life. Progressive course was found in 60.9 % of patients. Vitiligo vulgaris (57.8%) was most common morphological type. Most common site of onset (41.5%) and involvement (75.7%) was lower limb. Family history was present in 20.4%. CONCLUSIONS: Vitiligo constitutes important dermatological disease especially in India. The data suggest that local epidemiological behavior of vitiligo need not be the same across different regions. Vitiligo differs substantially in various clinical aspects.

Actinic keratosis underlying cutaneous horn at an unusual site-a case report.

Cutaneous horns are usually found on chronic sun-damaged skin. A cutaneous horn is a rare tumour, often conical, circumscribed, and composed of dead keratin usually derived from base keratinocytes. It occurs mainly in association with underlying benign, premalignant, and malignant cutaneous diseases. The commonest malignancy is squamous cell carcinoma. Thus, to accurately ascertain the nature of the condition at the base of the lesion and to rule out malignancy, an excision biopsy is indicated. Here, we report a case of cutaneous horn over the palmar aspect of the left middle finger in a 45-year-old man whose histopathology showed actinic keratosis.

Supramolecular BODIPY-Zn(II)-bisporphyrin dyad and trinitrofluorenone encapsulated triad as models of antenna-reaction center: synthesis, structure and photophysical properties.

We describe the synthesis, characterization and photophysical properties of the dyads Zn2DEP·TNF (1) and Zn2DEP·2Py-BDP (2) and triad Zn2DEP·2Py-BDP·TNF (3), which enable us to investigate the changes in the spectroscopic properties upon the axial coordination of pyridine substituted bodipy (Py-BDP) to Zn2DEP in the dyads and the further encapsulation of TNF in the triad. Zn2DEP·TNF (1) is structurally characterized while the other compounds, Py-BDP, 2 and 3, are geometrically optimized using DFT in the absence of X-ray crystallography. It has been found that the encapsulated TNF guest within the bisporphyrin cavity is involved in strong π-π interactions with the host resulting in robust host-guest assemblies that also retain the structural integrity in solution for a long time. The association constants, K, between the host and guests are calculated at 298 K by measuring the change in the fluorescence emission in solution and are found to be 1.0 × 10(7) M(-2) for the 1 : 2 binding in 2 and 1.2 × 10(3) M(-1) for the 1 : 1 binding in 3. The solution (1)H NMR spectrum of the supramolecular dyad 2 shows an upfield shift of the Py-BDP protons due to the strong ring current of the porphyrin rings. Similarly, upon the encapsulation of TNF in triad 3, the guest protons undergo an upfield shift owing to the ring current effect. Electrochemical studies of dyad 2 indicate that the Py-BDP and Zn-bisporphyrin subunits in the dyads interact very weakly. The negative and positive shifts of the reduction and oxidation potentials indicate that it is difficult to reduce/oxidize the encapsulated complex 3. The steady state emission spectrum shows that the fluorescence intensity of the axially coordinated Py-BDP in 2 (excited at 500 nm) is remarkably quenched in comparison to free Py-BDP due to efficient photoinduced intramolecular singlet-to-singlet energy transfer from the excited state of Py-BDP to the zinc-bisporphyrin in 2. The remarkable quenching of the fluorescence intensity of Py-BDP upon excitation at 500 nm in 3 is due to photoinduced electron transfer from the excited states of Py-BDP to TNF, which is also thermodynamically favorable. The location of the electron densities on the HOMO and LUMO further support the formation of a charge-separated state in which the zinc-bisporphyrin acts as an electron donor whilst TNF acts as an electron acceptor in the supramolecular triad 3. The electrochemically evaluated HOMO-LUMO gap also maintains a good agreement with the computed HOMO-LUMO gap.

Sweat gland adenocarcinoma of scalp.

Sweat gland adenocarcinoma is a rare tumor particularly over scalp. They have potential to be benign as well as distant metastasis. Usually presents with papules or nodules. Ulcerative morphology is uncommon. Wide surigical excision with regional lymph not dissection is the treatment of choice. A 42-year-old female with sweat gland adenocarcinoma of scalp is reported with cervical lymph node involvement.

Encapsulation of TCNQ and the acridinium ion within a bisporphyrin cavity: synthesis, structure, and photophysical and HOMO-LUMO-gap-mediated electron-transfer properties.

The encapsulation of tetracyanoquinodimethane (TCNQ) and fluorescent probe acridinium ions (AcH(+)) by diethylpyrrole-bridged bisporphyrin (H(4)DEP) was used to investigate the structural and spectroscopic changes within the bisporphyrin cavity upon substrate binding. X-ray diffraction studies of the bisporphyrin host (H(4)DEP) and the encapsulated host-guest complexes (H(4)DEP⋅TCNQ and [H(4)DEP⋅AcH]ClO(4)) are reported. Negative and positive shifts of the reduction and oxidation potentials, respectively, indicated that it was difficult to reduce/oxidize the encapsulated complexes. The emission intensities of bisporphyrin, upon excitation at 560 nm, were quenched by about 65 % and 95 % in H(4)DEP⋅TCNQ and [H(4)DEP⋅AcH]ClO(4), respectively, owing to photoinduced electron transfer from the excited state of the bisporphyrin to TCNQ/AcH(+); this result was also supported by DFT calculations. Moreover, the fluorescence intensity of encapsulated AcH(+) (excited at 340 nm) was also remarkably quenched compared to the free ions, owing to photoinduced singlet-to-singlet energy transfer from AcH(+) to bisporphyrin. Thus, AcH(+) acted as both an acceptor and a donor, depending on which part of the chromophore was excited in the host-guest complex. The electrochemically evaluated HOMO-LUMO gap was 0.71 and 1.42 eV in H(4)DEP⋅TCNQ and [H(4)DEP⋅AcH]ClO(4), respectively, whilst the gap was 2.12 eV in H(4)DEP. The extremely low HOMO-LUMO gap in H(4)DEP⋅TCNQ led to facile electron transfer from the host to the guest, which was manifested in the lowering of the CN stretching frequency (in the solid state) in the IR spectra, a strong radical signal in the EPR spectra at 77 K, and also the presence of low-energy bands in the UV/Vis spectra (in the solution phase). Such an efficient transfer was only possible when the donor and acceptor moieties were in close proximity to one another.

Efficient complexation of pyrrole-bridged dizinc(II) bisporphyrin with fluorescent probe pyrene: synthesis, structure, and photoinduced singlet-singlet energy transfer.

A diethylpyrrole-bridged dizinc(II) bisporphyrin (Zn(2)DEP) is reported that encapsulates fluorescent probe pyrene molecules through strong π-π interactions, which can relay information about the chemical environment in the interior of the host-guest supramolecular assembly. X-ray structures of both Zn(2)DEP and the encapsulated pyrene complex are reported, which provides a rare opportunity to investigate the structural changes upon guest binding. A comparative structural analysis demonstrated the exceptional ability of this bisporphyrin platform to open its binding pocket for pyrene encapsulation by a vertical displacement of more than 2.45 Å, although both Zn(2)DEP and the pyrene complex have nearly parallel porphyrin ring orientations. The (1)H NMR spectrum of the encapsulated pyrene complex in solution shows the upfield shifts of the pyrene protons due to a strong ring current effect, which demonstrates the retention of the solid-state structure in solution. To further assess the extent to which pyrene guests remain encapsulated in solution, a known fluorescence quencher, dimethylaniline, was added to the host-guest assembly, which shows no exciplex formation for days in nonpolar solvents. Thus, the assembly also retained the structural integrity in solution for a long time. The association constant (K(asso)) for such a complexation process in solution was observed to be 1.78×10(5) M(-2) for 1:2 binding. Steady-state fluorescence and lifetime studies indicate significant photoinduced singlet-singlet energy transformation from the excited state of pyrene to zinc bisporphyrin.

Axial ligand orientations in a distorted porphyrin macrocycle: synthesis, structure, and properties of low-spin bis(imidazole)iron(III) and iron(II) porphyrinates.

We have reported here, for the first time, the parallel and perpendicular orientation preferences of two planar and unhindered imidazoles as axial ligands (L) while coordinated toward iron(III) and iron(II) porphyrins, respectively, in a nonplanar porphyrinic environment. The synthesis and characterization of low-spin Fe(III)(tn-OEP)(L)(2) x ClO(4) and Fe(II)(tn-OEP)(L)(2) are reported. Fe(III)(tn-OEP)(L)(2) x ClO(4) shows rhombic electron paramagnetic resonance (EPR) spectra (at 77 K) in both solid and solution phases that are very characteristic for low-spin (S = 1/2) iron porphyrins with two axial imidazole ligands aligned parallel to each other. Single-point energy calculation is also performed on Fe(III)(tn-OEP)(1-MeIm)(2)(+) using density functional theory (DFT), which shows that the relative parallel orientations of two 1-MeIm are more stable than the perpendicular orientations. X-ray structures of Fe(II)(tn-OEP)(1-MeIm)(2) and Fe(II)(tn-OEP)(1-MeIm)(2).THF are reported that demonstrate, for the first time, the near-perpendicular axial ligand orientation (80.9 and 89.8 degrees, respectively) for iron(II) porphyrins in a distorted macrocyclic environment. Even starting from parallel axial orientations of 1-MeIm, geometry optimization using DFT converged well to the perpendicular axial alignment with a 82.54 degree dihedral angle, which is in close agreement with experiment. This is in sharp contrast to all earlier reports, in which sterically crowded imidazole (such as 2-MeIm) or a nearly planar porphyrin core with a "picket fence" environment that restricts the rotation of the axial ligands is required for perpendicular orientation. Electrochemical data obtained from a cyclic voltammetric study for Fe(II)(tn-OEP)(L)(2) reveal one-electron oxidation at very high positive potential, which readily explains why the complexes are so stable in air. Bulk oxidation of Fe(II)(tn-OEP)(1-MeIm)(2) at a constant potential of 0.69 V in dichloromethane with 0.1 M tetrabutylammonium perchlorate as the supporting electrolyte generates Fe(III)(tn-OEP)(1-MeIm)(2) x ClO(4), which has the same EPR spectrum and which upon reduction at 0.29 V regenerates Fe(II)(tn-OEP)(1-MeIm)(2) again. Thus, we have demonstrated here, for the first time, that iron(II) and iron(III) porphyrinates with two planar and unhindered axial imidazoles have different orientation preferences in a nonplanar porphyrinic environment.

Modulation of metal displacements in a saddle distorted macrocycle: synthesis, structure, and properties of high-spin Fe(III) porphyrins and implications for the hemoproteins.

A rare family of five and six-coordinated high-spin Fe(III) porphyrins incorporating weak axial ligands are synthesized and structurally characterized which demonstrate, for the first time, stepwise metal displacements in a single distorted macrocyclic environment that has generally been seen in many biological systems. The introduction of four nitro groups into the meso-positions of octaethyl porphyrin severely distorts the porphyrin geometry and provides an interesting modulation of the macrocycle properties which enables the facile isolation of "pure" high-spin Fe(III)(tn-OEP)Cl, Fe(III)(tn-OEP)(MeOH)Cl, and Fe(III)(tn-OEP)(H2O)2(+) in excellent yields in a saddle distorted macrocyclic environment that are known to stabilize intermediate spin states. The stepwise out-of-plane displacements of iron are as follows: 0.47 A for Fe(III)(tn-OEP)Cl; 0.09 A for Fe(III)(tn-OEP)(MeOH)Cl, and 0.01 A for Fe(III)(tn-OEP)(H2O)2(+) from the mean plane of the porphyrins. However, in both five and six-coordinated Fe(III) porphyrins, the Fe-Np distances are quite comparable while the porphyrin cores have expanded significantly, virtually to the same extent for the six-coordinate complexes reported here. The large size of the high-spin iron(III) atom in Fe(III)(tn-OEP)(H2O)2(+) is accommodated perfectly with no displacement of the metal. This expansion is accompanied by a significant decrease of the saddle distortion with a clear increase of the ruffling. Furthermore, the Fe atom in Fe(III)(tn-OEP)(MeOH)Cl is not out of plane because of the larger atom size; however, the displacement of the iron depends on both the relative strength of the axial ligands, as well as the nature and extent of the ring deformation. Our characterization demonstrates that increase in ruffling and/or decrease in macrocycle deformation brings the iron atom more into the plane in a distorted macrocyclic environment. Our observations thus suggest that the displacements of iron in proteins are the consequences of nonequivalent axial coordination, as well as protein induced deformations at the heme. The high-spin nature of the complexes reported here is believed to be due to the larger Fe-Np distances which then reduce substantially the interaction between iron d(x2)-y2 and porphyrin a(2u) orbital. The Fe(III)/Fe(II) reduction potential of Fe(III)(tn-OEP)Cl shows a reversible peak at large positive value (0.20 V), and no ring-centered oxidation was observed within the solvent limit (approximately 1.80 V). It is thus easier to reduce Fe(III)(tn-OEP)Cl by almost 700 mV compared to Fe(III)(OEP)Cl while oxidations are very difficult. Furthermore, the addition of 3-Cl-pyridine to Fe(III)(tn-OEP)Cl in air undergoes spontaneous auto reduction to produce the rare air-stable Fe(II)(tn-OEP)(3-Cl-py)2 that shows Fe(II)/Fe(III) oxidation peaks at high positive potential (0.79 V), which is approximately 600 mV more anodic compared to [Fe(II)(tn-OEP)Cl](-). This large anodic shift illustrates the effective removal of metal-centered electron density by the macrocycle when the metal is constrained to reside in the porphyrin plane.