Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State.

The solid-state properties of organic radicals depend on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4-dimethoxyphenylene), which associates in its bisradical dicationic redox state with the methyl viologen radical cation (MV•+) to give a 1:1 inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments reveal that the methoxy substituents on the p-phenylene linkers do not influence binding of the cyclophane toward small neutral guests-such as dimethoxybenzene and tetrathiafulvalene-whereas binding of larger radical cationic guests such as MV•+ by the reduced cyclophane decreases 10-fold. X-ray diffraction analysis reveals that the solid-state superstructure of the 1:1 complex constitutes a discrete entity with weak intermolecular orbital overlap between neighboring complexes. Transient nutation EPR experiments and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap, while the quartet-state spin configuration is higher in energy and inaccessible at ambient temperature. Superconducting quantum interference device (SQUID) measurements reveal that the trisradical tricationic complexes interact antiferromagnetically and form a one-dimensional Heisenberg antiferromagnetic chain along the a-axis of the crystal. These results offer insights into the design and synthesis of organic magnetic materials based on host-guest complexes.

Effect of Goal-directed Hemodynamic Therapy in Postcardiac Surgery Patients.

BACKGROUND AND AIMS: Early goal-directed therapy (EGDT) provides preset goals to be achieved by intravenous fluid therapy and inotropic therapy with earliest detection of change in the hemodynamic profile. Improved outcome in cardiac surgery patients has been shown by perioperative volume optimization, while postoperative intensive care unit (ICU) stay can be decreased by improving oxygen delivery. Our aim of this study was to study the outcome of EGDT in patients undergoing elective cardiac surgery. MATERIALS AND METHODS: This is a prospective single institute study involving a total of 478 patients. Patients were divided into group I, who received standard hospital care, and group II, who received EGDT. Postoperatively, patients were observed in ICU for 72 hours. Hemodynamics, laboratory data, fluid bolus, inotrope score, complication, ventilatory time, and mortality data were collected. RESULTS: Postoperative ventilatory period (11.12 ± 10.11 vs 9.45 ± 8.87, p = 0.0719) and frequency of change in inotropes (1.900 ± 0.9 vs 1.19 ± 0.61, p = 0.0717) were lower in group II. Frequency of crystalloid boluses (1.33 ± 0.65 vs 1.75 ± 1.09, p = 0.0126), and quantity of packed cell volume (PCV) used (1.63 ± 1.03 vs 2.04 ± 1.42, p = 0.0364) were highly significant in group II. Use of colloids was higher in group II and was statistically significant (1.98 ± 1.99 vs 3.05 ± 2.17, p = 0.0012). The acute kidney injury (AKI) rate was (58 (23.10%) vs 30 (13.21%), p = 0.007) lower and statistically significant (p = 0.007) in group II. CONCLUSION: Early goal-directed therapy reduces the postoperative ventilatory period, frequency of changes in inotropes, and incidence of AKI, and decreases ventilation hours, number of times inotropes changed, and AKI. HOW TO CITE THIS ARTICLE: Patel H, Parikh N, Shah R, Patel R, Thosani R, Shah P, et al. Effect of Goal-directed Hemodynamic Therapy in Postcardiac Surgery Patients. Indian J Crit Care Med 2020;24(5):321-326.

Discrete Dimers of Redox-Active and Fluorescent Perylene Diimide-Based Rigid Isosceles Triangles in the Solid State.

The development of rigid covalent chiroptical organic materials, with multiple, readily available redox states, which exhibit high photoluminescence, is of particular importance in relation to both organic electronics and photonics. The chemically stable, thermally robust, and redox-active perylene diimide (PDI) fluorophores have received ever-increasing attention owing to their excellent fluorescence quantum yields in solution. Planar PDI derivatives, however, generally suffer from aggregation-caused emission quenching in the solid state. Herein, we report on the design and synthesis of two chiral isosceles triangles, wherein one PDI fluorophore and two pyromellitic diimide (PMDI) or naphthalene diimide (NDI) units are arranged in a rigid cyclic triangular geometry. The optical, electronic, and magnetic properties of the rigid isosceles triangles are fully characterized by a combination of optical spectroscopies, X-ray diffraction (XRD), cyclic voltammetry, and computational modeling techniques. Single-crystal XRD analysis shows that both isosceles triangles form discrete, nearly cofacial PDI-PDI π-dimers in the solid state. While the triangles exhibit fluorescence quantum yields of almost unity in solution, the dimers in the solid state exhibit very weak-yet at least an order of magnitude higher-excimer fluorescence yield in comparison with the almost completely quenched fluorescence of a reference PDI. The triangle containing both NDI and PDI subunits shows superior intramolecular energy transfer from the lowest excited singlet state of the NDI to that of the PDI subunit. Cyclic voltammetry suggests that both isosceles triangles exhibit multiple, easily accessible, and reversible redox states. Applications beckon in arenas related to molecular optoelectronic devices.

The effect of spray drying on the difference in flavor and functional properties of liquid and dried whey proteins, milk proteins, and micellar casein concentrates.

Traditionally most protein ingredients are sold as a powder due to transport ease and longer shelf life. Many high-protein powder ingredients such as milk protein concentrate with 85% protein and micellar casein concentrate have poor rehydration properties (e.g., solubility) after storage, which might limit their use. An alternative to the production of dried protein ingredients is the option to use liquid protein ingredients, which saves the cost of spray drying, but may also improve flavor and offer different functional properties. The objective of this study was to determine the effect of spray drying on the flavor and functionality of high-protein ingredients. Liquid and dried protein ingredients (whey protein concentrate with 80% protein, whey protein isolate, milk protein concentrate with 85% protein, and micellar casein concentrate) were manufactured from the same lot of milk at the North Carolina State University pilot plant. Functional differences were evaluated by measurement of foam stability and heat stability. Heat stability was evaluated by heating at 90°C for 0, 10, 20, and 30 min followed by micro-bicinchoninic acid and turbidity loss measurements. Sensory properties were evaluated by descriptive analysis, and volatile compounds were evaluated by gas chromatography-mass spectrometry. No differences were detected in protein heat stability between liquids and powders when spray dried under these conditions. Whey protein concentrate with 80% protein (liquid or spray dried) did not produce a foam. All powders had higher aroma intensity and cooked flavors compared with liquids. Powder proteins also had low but distinct cardboard flavor concurrent with higher relative abundance of volatile aldehydes compared with liquids. An understanding of how spray drying affects both flavor and functionality may help food processors better use the ingredients they have available to them.

Noninvasive Substitution of K+ Sites in Cyclodextrin Metal-Organic Frameworks by Li+ Ions.

Co-crystallization of K+ and Li+ ions with γ-cyclodextrin (γ-CD) has been shown to substitute the K+ ion sites partially by Li+ ions, while retaining the structural integrity and accessible porosity of CD-MOF-1 (MOF, metal-organic framework). A series of experiments, in which the K+/Li+ ratio was varied with respect to that of γ-CD, have been conducted in order to achieve the highest possible proportion of Li+ ions in the framework. Attempts to obtain a CD-MOF containing only Li+ ions resulted in nonporous materials. The structural occupancy on the part of the Li+ ions in the new CD-MOF has been confirmed by single-crystal X-ray analysis by determining the vacancies of K+-ion sites and accounting for the cation/γ-CD ratio in CD-MOF-1. The proportion of Li+ ions has also been confirmed by elemental analysis, whereas powder X-ray diffraction has established the stability of the extended framework. This noninvasive synthetic approach to generating mixed-metal CD-MOFs is a promising method for obtaining porous framework unattainable de novo. Furthermore, the CO2 and H2 capture capacities of the Li+-ion-substituted CD-MOF have been shown to exceed the highest sorption capacities reported so far for CD-MOFs.

Influence of hydrodynamic cavitation on the rheological properties and microstructure of formulated Greek-style yogurts.

With limited applications of acid whey generated during the manufacture of Greek yogurts, an alternate processing technology to sidestep the dewheying process was developed. Milk protein concentrate (MPC) and carbon dioxide-treated milk protein concentrate (TMPC) were used as sources of protein to fortify skim milk to 9% (wt/wt) protein for the manufacture of Greek-style yogurts (GSY). The GSY bases were inoculated and fermented with frozen direct vat set yogurt culture to a pH of 4.6. Owing to the difference in buffering of MPC and TMPC, GSY with TMPC and MPC exhibited different acidification kinetics, with GSY containing TMPC having a lower fermentation time. The GSY with TMPC had a titratable acidity of 1.45% lactic acid and was comparable to acidity of commercial Greek yogurt (CGY). Hydrodynamic cavitation at 4 different rotor speeds (0, 15, 30, and 60 Hz) as a postfermentation tool reduced the consistency coefficient (K) of GSY containing TMPC from 79.4 Pa·sn at 0 Hz to 17.59 Pa·sn at 60 Hz. Similarly for GSY containing MPC, K values decreased from 165.74 Pa·sn at 0 Hz to 53.04 Pa·sn at 60 Hz. The apparent viscosity (η100) was 0.25 Pa·s for GSY containing TMPC and 0.66 Pa·s for GSY containing MPC at 60 Hz. The CGY had a η100 value of 0.74 Pa·s. Small amplitude rheological analysis performed on GSY indicated a loss of elastic modulus dependency on frequency caused by the breakdown of protein interactions with increasing cavitator rotor speeds. A steady decrease in hardness and adhesiveness values of GSY was observed with increasing cavitational intensities. Numbers of grains with a perimeter of >1mm of cavitated GSY with TMPC and MPC were 35 and 13 grains/g of yogurt, respectively, and were lower than 293 grains/g observed in CGY. The water-holding capacity of GSY was higher than that observed for a commercial strained Greek yogurt. The ability to scale up the process of hydrodynamic cavitation industrially, and the ease of controlling events of cavitation that can influence final textural properties of the product, make this technology promising for large-scale industrial application. Overall, the current set of experiments employed in the manufacture of GSY, which included the use of TMPC as a protein source in conjunction with hydrodynamic cavitation, could help achieve comparable titratable acidity values, rheological properties, and microstructure to that of a commercial strained Greek yogurt.

Systematic Investigation of the Effect of Polymerization Routes on the Gas-Sorption Properties of Nanoporous Azobenzene Polymers.

Functional-group-oriented polymerization strategies have contributed significantly to the initial development of porous polymers and have led to the utilization of several well-known organic transformations in the synthesis of these polymers. Because there are multiple polymerization routes that can be used to introduce the same chemical functionality, it is very important to demonstrate the effect of different polymerization routes on the gas-sorption properties of these chemically similar polymers. Herein, we have studied the rich chemistry of azobenzenes and synthesized four chemically similar nanoporous azobenzene polymers (NABs) with surface areas of up to 1021 m(2) g(-1) . The polymerization routes have a significant impact on the pore-size distributions of the NABs, which directly affects the temperature dependence of the CO2 /N2 selectivity. A pore-width maximum of 6-8 Å, narrow pore-size distribution, and small particle size (20-30 nm) were very critical for high CO2 /N2 selectivity and N2 phobicity, which is associated with azo linkages and realized at warm temperatures. Our findings collectively suggest that an investigation of different polymerization routes for the same chemical functionalization is critical to understand fully the combined effect of textural properties, local environment, and chemical functionalization on the gas-sorption properties of nanoporous polymers.

Highly optimized CO2 capture by inexpensive nanoporous covalent organic polymers and their amine composites.

Carbon dioxide (CO2) storage and utilization requires effective capture strategies that limit energy penalties. Polyethylenimine (PEI)-impregnated covalent organic polymers (COPs) with a high CO2 adsorption capacity are successfully prepared in this study. A low cost COP with a high specific surface area is suitable for PEI loading to achieve high CO2 adsorption, and the optimal PEI loading is 36 wt%. Though the adsorbed amount of CO2 on amine impregnated COPs slightly decreased with increasing adsorption temperature, CO2/N2 selectivity is significantly improved at higher temperatures. The adsorption of CO2 on the sorbent is very fast, and a sorption equilibrium (10% wt) was achieved within 5 min at 313 K under the flow of simulated flue gas streams. The CO2 capture efficiency of this sorbent is not affected under repetitive adsorption-desorption cycles. The highest CO2 capture capacity of 75 mg g(-1) at 0.15 bar is achieved under dry CO2 capture however it is enhanced to 100 mg g(-1) in the mixed gas flow containing humid 15% CO2. Sorbents were found to be thermally stable up to at least 200 °C. TGA and FTIR studies confirmed the loading of PEIs on COPs. This sorbent with high and fast CO2 sorption exhibits a very promising application in direct CO2 capture from flue gas.

Modulation of red blood cell population dynamics is a fundamental homeostatic response to disease.

Increased red blood cell (RBC) volume variation (RDW) has recently been shown to predict a wide range of mortality and morbidity: death due to cardiovascular disease, cancer, infection, renal disease, and more; complications in heart failure and coronary artery disease, advanced stage and worse prognosis in many cancers, poor outcomes in autoimmune disease, and many more. The mechanisms by which all of these diseases lead to increased RDW are unknown. Here we use a semi-mechanistic mathematical model of in vivo RBC population dynamics to dissect the factors controlling RDW and show that elevated RDW results largely from a slight reduction in the in vivo rate of RBC turnover. RBCs become smaller as they age, and a slight reduction in the rate of RBC turnover allows smaller cells to continue circulating, expanding the low-volume tail of the RBC population's volume distribution, and thereby increasing RDW. Our results show that mildly extended RBC lifespan is a previously unrecognized homeostatic adaptation common to a very wide range of pathologic states, likely compensating for subtle reductions in erythropoietic output. A mathematical model-based estimate of the clearance rate may provide a novel early-warning biomarker for a wide range of morbidity and mortality.

Directing the structural features of N(2)-phobic nanoporous covalent organic polymers for CO(2) capture and separation.

A family of azo-bridged covalent organic polymers (azo-COPs) was synthesized through a catalyst-free direct coupling of aromatic nitro and amine compounds under basic conditions. The azo-COPs formed 3D nanoporous networks and exhibited surface areas up to 729.6 m(2) g(-1) , with a CO2 -uptake capacity as high as 2.55 mmol g(-1) at 273 K and 1 bar. Azo-COPs showed remarkable CO2 /N2 selectivities (95.6-165.2) at 298 K and 1 bar. Unlike any other porous material, CO2 /N2 selectivities of azo-COPs increase with rising temperature. It was found that azo-COPs show less than expected affinity towards N2 gas, thus making the framework "N2 -phobic", in relative terms. Our theoretical simulations indicate that the origin of this unusual behavior is associated with the larger entropic loss of N2 gas molecules upon their interaction with azo-groups. The effect of fused aromatic rings on the CO2 /N2 selectivity in azo-COPs is also demonstrated. Increasing the π-surface area resulted in an increase in the CO2 -philic nature of the framework, thus allowing us to reach a CO2 /N2 selectivity value of 307.7 at 323 K and 1 bar, which is the highest value reported to date. Hence, it is possible to combine the concepts of "CO2 -philicity" and "N2 -phobicity" for efficient CO2 capture and separation. Isosteric heats of CO2 adsorption for azo-COPs range from 24.8-32.1 kJ mol(-1) at ambient pressure. Azo-COPs are stable up to 350 °C in air and boiling water for a week. A promising cis/trans isomerization of azo-COPs for switchable porosity is also demonstrated, making way for a gated CO2 uptake.

Evaluation of ultrasound for central venous access in ICU by an in experienced trainee.

BACKGROUND AND AIMS: Central venous catheter placement is an important procedure for ICU (Intensive Care Unit) patients. We studied the usefulness of ultrasonography for placement of central venous catheter by in-experienced anesthetists. MATERIALS AND METHODS: A prospective observational study of 32 patients requiring central venous access (CVA) in surgical ICU (SICU). Data collected were patient's demographics, indication, type of catheter, success rate, attempts, complication rate and access time were recorded and compared with other studies. RESULT: The overall success rate was 89.5% in the IJV (Internal Jugular Vein) and 92.3% for SCV (Subclavian Vein) group. The success rates for insertion at first, second, and third attempt were 52.6%, 31.6%, and 5.2% for IJV and 46.2% and 53.8% for SCV. Average number of attempts made for IJV cannulation was 1.74 +/- 1.04 and 1.54 +/- 0.51 for SCV. The total time taken for IJV access was 858.78 +/- 381.9 sec, whereas in the SCV group, it was 984 +/- 328.98 seconds. In our study, overall rate of complication was 21.05% (4/19 patients) for IJV and 23.07% (3/13 patients) for SCV insertion. Incidence of various complications like arterial puncture, misplacement of CVC, hematoma, pneumothorax, and hemothorax were also noted. CONCLUSION: This study concludes that real time ultrasound guidance during IJV and SCV cannulation can achieve higher success rate, fewer complications, number of attempts, and failure rate among inexperienced anesthetists.

Estimating Glycemia From HbA1c and CGM: Analysis of Accuracy and Sources of Discrepancy.

OBJECTIVE: To examine the accuracy of different periods of continuous glucose monitoring (CGM), hemoglobin A1c (HbA1c), and their combination for estimating mean glycemia over 90 days (AG90). RESEARCH DESIGN AND METHODS: We retrospectively studied 985 CGM periods of 90 days with <10% missing data from 315 adults (86% of whom had type 1 diabetes) with paired HbA1c measurements. The impact of mean red blood cell age as a proxy for nonglycemic effects on HbA1c was estimated using published theoretical models and in comparison with empirical data. Given the lack of a gold standard measurement for AG90, we applied correction methods to generate a reference (eAG90) that we used to assess accuracy for HbA1c and CGM. RESULTS: Using 14 days of CGM at the end of the 90-day period resulted in a mean absolute error (95th percentile) of 14 (34) mg/dL when compared with eAG90. Nonglycemic effects on HbA1c led to a mean absolute error for average glucose calculated from HbA1c of 12 (29) mg/dL. Combining 14 days of CGM with HbA1c reduced the error to 10 (26) mg/dL. Mismatches between CGM and HbA1c >40 mg/dL occurred more than 5% of the time. CONCLUSIONS: The accuracy of estimates of eAG90 from limited periods of CGM can be improved by averaging with an HbA1c-based estimate or extending the monitoring period beyond ∼26 days. Large mismatches between eAG90 estimated from CGM and HbA1c are not unusual and may persist due to stable nonglycemic factors.

Hematologic setpoints are a stable and patient-specific deep phenotype.

The complete blood count is an important screening tool for healthy adults and is the most commonly ordered test at periodic physical exams. However, results are usually interpreted relative to one-size-fits-all reference intervals, undermining the goal of precision medicine to tailor medical care to the needs of individual patients based on their unique characteristics. Here we show that standard complete blood count indices in healthy adults have robust homeostatic setpoints that are patient-specific and stable, with the typical healthy adult's set of 9 blood count setpoints distinguishable from 98% of others, and with these differences persisting for decades. These setpoints reflect a deep physiologic phenotype, enabling improved detection of both acquired and genetic determinants of hematologic regulation, including discovery of multiple novel loci via GWAS analyses. Patient-specific reference intervals derived from setpoints enable more accurate personalized risk assessment, and the setpoints themselves are significantly correlated with mortality risk, providing new opportunities to enhance patient-specific screening and early intervention. This study shows complete blood count setpoints are sufficiently stable and patient-specific to help realize the promise of precision medicine for healthy adults.

Computer vision quantitation of erythrocyte shape abnormalities provides diagnostic, prognostic, and mechanistic insight.

Examination of red blood cell (RBC) morphology in peripheral blood smears can help diagnose hematologic diseases, even in resource-limited settings, but this analysis remains subjective and semiquantitative with low throughput. Prior attempts to develop automated tools have been hampered by their poor reproducibility and limited clinical validation. Here, we present a novel, open-source machine-learning approach (denoted as RBC-diff) to quantify abnormal RBCs in peripheral smear images and generate an RBC morphology differential. RBC-diff cell counts showed high accuracy for single-cell classification (mean AUC, 0.93) and quantitation across smears (mean R2, 0.76 compared with experts, interexperts R2, 0.75). RBC-diff counts were concordant with the clinical morphology grading for 300 000+ images and recovered the expected pathophysiologic signals in diverse clinical cohorts. Criteria using RBC-diff counts distinguished thrombotic thrombocytopenic purpura and hemolytic uremic syndrome from other thrombotic microangiopathies, providing greater specificity than clinical morphology grading (72% vs 41%; P < .001) while maintaining high sensitivity (94% to 100%). Elevated RBC-diff schistocyte counts were associated with increased 6-month all-cause mortality in a cohort of 58 950 inpatients (9.5% mortality for schist. >1%, vs 4.7% for schist; <0.5%; P < .001) after controlling for comorbidities, demographics, clinical morphology grading, and blood count indices. RBC-diff also enabled the estimation of single-cell volume-morphology distributions, providing insight into the influence of morphology on routine blood count measures. Our codebase and expert-annotated images are included here to spur further advancement. These results illustrate that computer vision can enable rapid and accurate quantitation of RBC morphology, which may provide value in both clinical and research contexts.

Assessment of the effect of two regimens of milrinone infusion in paediatric patients with pulmonary artery hypertension undergoing corrective cardiac procedure: A prospective observational study.

Background: The aim of the study was to compare the effect of two different regimens of milrinone in pediatric patients with pulmonary artery hypertension (PAH) undergoing corrective procedure. Materials and Methods: This randomized prospective study included 100 pediatric patients undergoing corrective cardiac surgeries. Group E: Milrinone was started as infusion 0.5 µg/kg/min without a loading dose after induction of anesthesia and continued as infusion 0.5-0.75 µg/kg/min in the pediatric cardiac surgical intensive care unit (PSICU). Group L: Milrinone was started as a loading dose 50 µg/kg over 10 min before weaning from cardiopulmonary bypass (CPB) followed by infusion 0.5-0.75 µg/kg/min in the PSICU. We compared heart rate, mean arterial blood pressure, central venous pressure, cardiac index (CI), mean pulmonary arterial pressure (MPAP), serum lactate level, urine output, vasoactive inotropic score, mechanical ventilation duration, and intensive care unit (ICU)- and hospital length of stay between the groups. Results: There was an increase in mean arterial blood pressure, CI, and urine output in Group E compared to Group L (P < 0.05). MPAP, serum lactate level, and requirement of inotropes and vasopressors were lower in Group E compared to Group L (P < 0.05). Mechanical ventilation duration, ICU, and hospital length of stay were shorter in Group E than Group L (P < 0.05). Conclusions: Early use of milrinone in patients with PAH undergoing corrective cardiac surgeries improved CI and mean arterial pressure, decreased MPAP, improved urine output, decreased serum lactate level, and decreased requirement of inotropes and vasopressors after weaning from CPB compared to the milrinone bolus group.

Organically modified layered magnesium silicates to improve rheology of reservoir drilling fluids.

Petroleum well drilling fluids are one of the most significant constituents in the subterranean drilling processes to meet an increasing global demand for oil and gas. Drilling fluids experience exceptional wellbore conditions, e.g. high temperature and high pressure that adversely affect the rheology of these fluids. Gas and oil well drilling operations have to adjourn due to changes in fluid rheology, since the drilling fluids may lose their effectiveness to suspend heavy particles and to carry drilled cuttings to the surface. The rheological properties of drilling fluids can be controlled by employing viscosifiers that should have exceptional stability in downhole environments. Here, we have developed next-generation viscosifiers-organically modified magnesium silicates (MSils)-for reservoir drilling fluids where organic functionalities are directly linked through the Si-C bond, unlike the industry's traditional viscosifier, organoclay, that has electrostatic linkages. The successful formation of covalently-linked hexadecyl and phenyl functionalized magnesium silicates (MSil-C16 and MSil-Ph) were confirmed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). Identical drilling fluid formulations were designed for comparison using MSils and a commercial viscosifier. The rheological properties of fluids were measured at ambient conditions as well as at high temperatures (up to 150 °C) and high pressure (70 MPa). Owing to strong covalent linkages, drilling fluids that were formulated with MSils showed a 19.3% increase in yield point (YP) and a 31% decrease in apparent viscosity (AV) at 150 °C under 70 MPa pressure, as compared to drilling fluids that were formulated with traditional organoclay. The higher yield point and lower apparent viscosity are known to facilitate and increased drilling rate of penetration of the fluids and an enhanced equivalent circulation density (ECD), the dynamic density condition, for efficient oil and gas wells drilling procedures.

Synthesis of highly dispersed gold and silver nanoparticles anchored on surfactant intercalated montmorillonite.

Gold and silver nanoparticles anchored on surfactant intercalated montmorillonite were prepared by two methodologies. In the first case, gold and silver nanoparticles were synthesized by reduction of gold and silver salt in hexadecyltrimethylammonium bromide (HDTA) and dioctadecyldimethylammonium chloride (DODA), followed by exchange of HDTA and DODA solution containing gold and silver nanoparticles into montmorillonite (MMT). In second case, HDTA and DODA with gold and silver salt was exchanged with MMT, and then reduced to obtain gold and silver nanoparticles. The particle size of gold and silver varies with the path of reduction as well as type of surfactant used for the modification of MMT. Gold and silver nanoparticles synthesized using quaternary ammonium salt with two long alkyl chain resulted into finer particles than a single long alkyl chain. The present study demonstrates the effect of reduction path, type of surfactants, and concentration of gold and silver on the particle size of gold and silver nanoparticles anchored on organoclay. Gold and silver nanoparticles supported organoclay were characterized by High resolution transmission electron microscopy (HRTEM), powdered X-ray diffraction (PXRD) and Inductive coupled plasma-atomic emission spectroscopy (ICP-AES).

Proton Conduction in Tröger's Base-Linked Poly(crown ether)s.

Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host-guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers-poly(TBL-DB18C6)- t and poly(TBL-DB18C6)- c-synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)- t, which is found to be 1.4 × 10-4 mS cm-1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

Pharmaceutical impurities: regulatory perspective for Abbreviated New Drug Applications.

Impurities in drug substances and drug products have been important regulatory issues in the Office of Generic Drugs by having significant impact on the approvability of Abbreviated New Drug Application (ANDAs). This review begins with a discussion of ANDAs and its similarity/differences with NDAs, highlighting the importance of control of pharmaceutical impurities in generic drug product development and regulatory assessment. An overview of the FDA draft guidance documents "ANDAs: Impurities in Drug Substances" and "ANDAs: Impurities in Drug Products" are provided. This introduces the identification and qualification procedures for ANDAs and approaches to the establishment of acceptance criteria for both drug substance and drug product. Case studies included in this review illustrate the proposed pathway for determination of impurities and their acceptance criteria, based upon the general principles of these guidances.

Effect of hydrogen peroxide on improving the heat stability of whey protein isolate solutions.

Whey protein isolate (WPI) solutions (12.8%w/w protein) were treated with varying concentrations of H2O2 in the range of 0-0.144 H2O2 to protein ratios (HTPR) by the addition of the required quantity of H2O2 and deionized water. The samples were analyzed for heat stability, rheological properties, denaturation level of ß-lactoglobulin (ß-LG) and α-lactalbumin (α-LA). The samples treated with H2O2 concentration >0.072 (HTPR) showed significant improvement in the heat stability, and decreased whey protein denaturation and aggregation. The WPI solution treated with H2O2 (>0.072 HTPR) remained in the liquid state after heat treatment at 120°C, whereas the control samples formed gel upon heat treatment. Detailed analysis of these samples suggested that the improvement in the heat stability of H2O2 treated WPI solution was attributed to the significant reduction in the sulfhydryl-disulfide interchange reaction during denaturation of ß-LG and α-LA.