21 CFR 1313.12 - Requirement of authorization to import.

Code of Federal Regulations, 2013 CFR

2013-04-01

... EXPORTATION OF LIST I AND LIST II CHEMICALS Importation of Listed Chemicals § 1313.12 Requirement of authorization to import. (a) Each regulated person who imports a listed chemical that meets or exceeds the threshold quantities identified in § 1310.04(f) or is a listed chemical for which no threshold has been...

Ultralow energy ion beam surface modification of low density polyethylene.

PubMed

Shenton, Martyn J; Bradley, James W; van den Berg, Jaap A; Armour, David G; Stevens, Gary C

2005-12-01

Ultralow energy Ar+ and O+ ion beam irradiation of low density polyethylene has been carried out under controlled dose and monoenergetic conditions. XPS of Ar+-treated surfaces exposed to ambient atmosphere show that the bombardment of 50 eV Ar+ ions at a total dose of 10(16) cm(-2) gives rise to very reactive surfaces with oxygen incorporation at about 50% of the species present in the upper surface layer. Using pure O+ beam irradiation, comparatively low O incorporation is achieved without exposure to atmosphere (approximately 13% O in the upper surface). However, if the surface is activated by Ar+ pretreatment, then large oxygen contents can be achieved under subsequent O+ irradiation (up to 48% O). The results show that for very low energy (20 eV) oxygen ions there is a dose threshold of about 5 x 10(15) cm(-2) before surface oxygen incorporation is observed. It appears that, for both Ar+ and O+ ions in this regime, the degree of surface modification is only very weakly dependent on the ion energy. The results suggest that in the nonequilibrium plasma treatment of polymers, where the ion flux is typically 10(18) m(-2) s(-1), low energy ions (<50 eV) may be responsible for surface chemical modification.

Chemical methods for encoding and decoding of posttranslational modifications

PubMed Central

Chuh, Kelly N.; Batt, Anna R.; Pratt, Matthew R.

2016-01-01

A large array of posttranslational modifications can dramatically change the properties of proteins and influence different aspects of their biological function such as enzymatic activity, binding interactions, and proteostasis. Despite the significant knowledge that has been gained about the function of posttranslational modifications using traditional biological techniques, the analysis of the site-specific effects of a particular modification, the identification of the full compliment of modified proteins in the proteome, and the detection of new types of modifications remains challenging. Over the years, chemical methods have contributed significantly in both of these areas of research. This review highlights several posttranslational modifications where chemistry-based approaches have made significant contributions to our ability to both prepare homogeneously modified proteins and identify and characterize particular modifications in complex biological settings. As the number and chemical diversity of documented posttranslational modifications continues to rise, we believe that chemical strategies will be essential to advance the field in years to come. PMID:26933738

Nano-Charged Polypropylene Application: Realistic Perspectives for Enhancing Durability

PubMed Central

Naddeo, Carlo; Vertuccio, Luigi; Barra, Giuseppina; Guadagno, Liberata

2017-01-01

Isotactic polypropylene/multi-walled carbon nanotube (iPP/MWCNTs) films have been exposed to accelerated weathering in a UV device for increasing times. The effect of UV irradiation on the structural and chemical changes has been investigated. The resistance to accelerated photooxidation of (iPP/MWCNTs) films has been compared to the photooxidation behaviour of unfilled polypropylene films with the same structural organization. The chemical and structural modifications resulting from photooxidation have been followed using infrared spectroscopy, calorimetric and diffractometric analysis. MWCNTs embedded in the polymeric matrix are able to strongly contrast the degradation mechanisms and the structural and morphological rearrangements caused by the UV treatment on the unfilled polymer. MWCNTs determine an induction period (IP) before the increase of the carbonyl and hydroxyl groups. The extent of the IP is strictly correlated to the amount of MWCNTs. The low electrical percolation threshold (EPT) and the electrical conductivity of the nanocomposites, together with their excellent thermal and photooxidative stability, make them promising candidates to fulfill many industrial requirements. PMID:28805728

40 CFR 372.25 - Thresholds for reporting.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW... threshold amounts for purposes of reporting under § 372.30 for toxic chemicals are as follows: (a) With respect to a toxic chemical manufactured (including imported) or processed at a facility during the...

40 CFR 372.25 - Thresholds for reporting.

Code of Federal Regulations, 2011 CFR

2011-07-01

... PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW... threshold amounts for purposes of reporting under § 372.30 for toxic chemicals are as follows: (a) With respect to a toxic chemical manufactured (including imported) or processed at a facility during the...

Effect of Age and Severity of Facial Palsy on Taste Thresholds in Bell's Palsy Patients

PubMed Central

Park, Jung Min; Kim, Myung Gu; Jung, Junyang; Kim, Sung Su; Jung, A Ra; Kim, Sang Hoon

2017-01-01

Background and Objectives To investigate whether taste thresholds, as determined by electrogustometry (EGM) and chemical taste tests, differ by age and the severity of facial palsy in patients with Bell's palsy. Subjects and Methods This study included 29 patients diagnosed with Bell's palsy between January 2014 and May 2015 in our hospital. Patients were assorted into age groups and by severity of facial palsy, as determined by House-Brackmann Scale, and their taste thresholds were assessed by EGM and chemical taste tests. Results EGM showed that taste thresholds at four locations on the tongue and one location on the central soft palate, 1 cm from the palatine uvula, were significantly higher in Bell's palsy patients than in controls (p<0.05). In contrast, chemical taste tests showed no significant differences in taste thresholds between the two groups (p>0.05). The severity of facial palsy did not affect taste thresholds, as determined by both EGM and chemical taste tests (p>0.05). The overall mean electrical taste thresholds on EGM were higher in younger Bell's palsy patients than in healthy subjects, with the difference at the back-right area of the tongue differing significantly (p<0.05). In older individuals, however, no significant differences in taste thresholds were observed between Bell's palsy patients and healthy subjects (p>0.05). Conclusions Electrical taste thresholds were higher in Bell's palsy patients than in controls. These differences were observed in younger, but not in older, individuals. PMID:28417103

6 CFR 27.203 - Calculating the screening threshold quantity by security issue.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 6 Domestic Security 1 2014-01-01 2014-01-01 false Calculating the screening threshold quantity by security issue. 27.203 Section 27.203 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CHEMICAL FACILITY ANTI-TERRORISM STANDARDS Chemical Facility Security Program § 27.203 Calculating the screening threshold quantity by...

6 CFR 27.203 - Calculating the screening threshold quantity by security issue.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 6 Domestic Security 1 2011-01-01 2011-01-01 false Calculating the screening threshold quantity by security issue. 27.203 Section 27.203 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CHEMICAL FACILITY ANTI-TERRORISM STANDARDS Chemical Facility Security Program § 27.203 Calculating the screening threshold quantity by...

6 CFR 27.203 - Calculating the screening threshold quantity by security issue.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 6 Domestic Security 1 2013-01-01 2013-01-01 false Calculating the screening threshold quantity by security issue. 27.203 Section 27.203 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CHEMICAL FACILITY ANTI-TERRORISM STANDARDS Chemical Facility Security Program § 27.203 Calculating the screening threshold quantity by...

6 CFR 27.203 - Calculating the screening threshold quantity by security issue.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 6 Domestic Security 1 2010-01-01 2010-01-01 false Calculating the screening threshold quantity by security issue. 27.203 Section 27.203 Domestic Security DEPARTMENT OF HOMELAND SECURITY, OFFICE OF THE SECRETARY CHEMICAL FACILITY ANTI-TERRORISM STANDARDS Chemical Facility Security Program § 27.203 Calculating the screening threshold quantity by...

General Characteristics of the Changes in the Thermal Stability of Proteins and Enzymes After the Chemical Modification of Their Functional Groups

NASA Astrophysics Data System (ADS)

Kutuzova, G. D.; Ugarova, N. N.; Berezin, Ilya V.

1984-11-01

The principal structural and physicochemical factors determining the stability of protein macromolecules in solution and the characteristics of the structure of the proteins from thermophilic microorganisms are examined. The mechanism of the changes in the thermal stability of proteins and enzymes after the chemical modification of their functional side groups and the experimental data concerning the influence of chemical modification on the thermal stability of proteins are analysed. The dependence of the stabilisation effect and of the changes in the structure of protein macromolecules on the degree of modification and on the nature of the modified groups and the groups introduced into proteins in the course of modification (their charge and hydrophobic properties) is demonstrated. The great practical value of the method of chemical modification for the preparation of stabilised forms of biocatalysts is shown in relation to specific examples. The bibliography includes 178 references.

Advances in chemical synthesis of structurally modified bioactive RNAs.

PubMed

Li, Ziyuan; Zhou, Haipin; Wu, Xiaoming; Yao, Hequan

2013-01-01

Methods for the chemical synthesis of RNA have been available for almost half century, and presently, RNA could be chemically synthesized by automated synthesizers, using protected ribonucleosides preactivated as phosphoramidites, which has already been covered by many reviews. In addition to advancement on synthetic methods, a variety of modifications have also been made on the synthesized oligonucleotides, and previous reviews on the general synthesis of RNAs have not covered this area. In this tutorial review, three types of modifications have been summarized standing at the viewpoint of medicinal chemistry: (1) modifications on nucleobase, comprising substituent introduction and replacement with pseudobase; (2) modifications on ribose, consisting of modifications on the 2', 3' or 5'-position, alternation of configuration, and conformational restriction on ribose; (3) modifications on internucleoside linkages, including amide, formacetal, sulfide, sulfone, ether, phosphorothiolate and phosphorothioate linkages. Synthetic methods achieving these modifications along with the functions or values of these modifications have also been discussed and commented on.

Preparation and properties of ZnS superhydrophobic surface with hierarchical structure

NASA Astrophysics Data System (ADS)

Yao, Lujun; Zheng, Maojun; He, Shuanghu; Ma, Li; Li, Mei; Shen, Wenzhong

2011-01-01

A novel ZnS hierarchical structure composed of nanorod arrays with branched nanosheets and nanowires grown on their upside walls, was synthesized over Au-coated silicon substrate via chemical vapor deposition technique. Contact angle and sliding angle of this hierarchical film with no surface modification were measured to be about 153.8° and 9.1° for 5 μl water droplets. Self-cleaning behavior and dynamic water-repelling performance were clearly demonstrated. In addition, electrowetting transition phenomenon from superhydrophobic to hydrophilic state happened when a critical bias ∼7.0 V was applied. Below this threshold voltage, the contact angle change is little. This work for the first time reports the creation of ZnS superhydrophobic surface and could enrich its research field as surface functional materials.

Ultrafast laser-induced modifications of energy bands of non-metal crystals

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2009-10-01

Ultrafast laser-induced variations of electron energy bands of transparent solids significantly influence ionization and conduction-band electron absorption driving the initial stage of laser-induced damage (LID). The mechanisms of the variations are attributed to changing electron functions from bonding to anti-bonding configuration via laser-induced ionization; laser-driven electron oscillations in quasi-momentum space; and direct distortion of the inter-atomic potential by electric field of laser radiation. The ionization results in the band-structure modification via accumulation of broken chemical bonds between atoms and provides significant contribution to the overall modification only when enough excited electrons are accumulated in the conduction band. The oscillations are associated with modification of electron energy by pondermotive potential of the oscillations. The direct action of radiation's electric field leads to specific high-frequency Franz-Keldysh effect (FKE) spreading the allowed electron states into the bands of forbidden energy. Those processes determine the effective band gap that is a laser-driven energy gap between the modified electron energy bands. Among those mechanisms, the latter two provide reversible band-structure modification that takes place from the beginning of the ionization and are, therefore, of special interest due to their strong influence on the initial stage of the ionization. The pondermotive potential results either in monotonous increase or oscillatory variations of the effective band gap that has been taken into account in some ionization models. The classical FKE provides decrease of the band gap. We analyzing the competition between those two opposite trends of the effective-band-gap variations and discuss applications of those effects for considerations of the laser-induced damage and its threshold in transparent solids.

Thresholds of Toxicological Concern for cosmetics-related substances: New database, thresholds, and enrichment of chemical space.

PubMed

Yang, Chihae; Barlow, Susan M; Muldoon Jacobs, Kristi L; Vitcheva, Vessela; Boobis, Alan R; Felter, Susan P; Arvidson, Kirk B; Keller, Detlef; Cronin, Mark T D; Enoch, Steven; Worth, Andrew; Hollnagel, Heli M

2017-11-01

A new dataset of cosmetics-related chemicals for the Threshold of Toxicological Concern (TTC) approach has been compiled, comprising 552 chemicals with 219, 40, and 293 chemicals in Cramer Classes I, II, and III, respectively. Data were integrated and curated to create a database of No-/Lowest-Observed-Adverse-Effect Level (NOAEL/LOAEL) values, from which the final COSMOS TTC dataset was developed. Criteria for study inclusion and NOAEL decisions were defined, and rigorous quality control was performed for study details and assignment of Cramer classes. From the final COSMOS TTC dataset, human exposure thresholds of 42 and 7.9 μg/kg-bw/day were derived for Cramer Classes I and III, respectively. The size of Cramer Class II was insufficient for derivation of a TTC value. The COSMOS TTC dataset was then federated with the dataset of Munro and colleagues, previously published in 1996, after updating the latter using the quality control processes for this project. This federated dataset expands the chemical space and provides more robust thresholds. The 966 substances in the federated database comprise 245, 49 and 672 chemicals in Cramer Classes I, II and III, respectively. The corresponding TTC values of 46, 6.2 and 2.3 μg/kg-bw/day are broadly similar to those of the original Munro dataset. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Thresholds in chemical respiratory sensitisation.

PubMed

Cochrane, Stella A; Arts, Josje H E; Ehnes, Colin; Hindle, Stuart; Hollnagel, Heli M; Poole, Alan; Suto, Hidenori; Kimber, Ian

2015-07-03

There is a continuing interest in determining whether it is possible to identify thresholds for chemical allergy. Here allergic sensitisation of the respiratory tract by chemicals is considered in this context. This is an important occupational health problem, being associated with rhinitis and asthma, and in addition provides toxicologists and risk assessors with a number of challenges. In common with all forms of allergic disease chemical respiratory allergy develops in two phases. In the first (induction) phase exposure to a chemical allergen (by an appropriate route of exposure) causes immunological priming and sensitisation of the respiratory tract. The second (elicitation) phase is triggered if a sensitised subject is exposed subsequently to the same chemical allergen via inhalation. A secondary immune response will be provoked in the respiratory tract resulting in inflammation and the signs and symptoms of a respiratory hypersensitivity reaction. In this article attention has focused on the identification of threshold values during the acquisition of sensitisation. Current mechanistic understanding of allergy is such that it can be assumed that the development of sensitisation (and also the elicitation of an allergic reaction) is a threshold phenomenon; there will be levels of exposure below which sensitisation will not be acquired. That is, all immune responses, including allergic sensitisation, have threshold requirement for the availability of antigen/allergen, below which a response will fail to develop. The issue addressed here is whether there are methods available or clinical/epidemiological data that permit the identification of such thresholds. This document reviews briefly relevant human studies of occupational asthma, and experimental models that have been developed (or are being developed) for the identification and characterisation of chemical respiratory allergens. The main conclusion drawn is that although there is evidence that the acquisition of sensitisation to chemical respiratory allergens is a dose-related phenomenon, and that thresholds exist, it is frequently difficult to define accurate numerical values for threshold exposure levels. Nevertheless, based on occupational exposure data it may sometimes be possible to derive levels of exposure in the workplace, which are safe. An additional observation is the lack currently of suitable experimental methods for both routine hazard characterisation and the measurement of thresholds, and that such methods are still some way off. Given the current trajectory of toxicology, and the move towards the use of non-animal in vitro and/or in silico) methods, there is a need to consider the development of alternative approaches for the identification and characterisation of respiratory sensitisation hazards, and for risk assessment. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Initial analyses of the relationship between 'Thresholds' of toxicity for individual chemicals and 'Interaction Thresholds' for chemical mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Raymond S.H.; Dennison, James E.

2007-09-01

The inter-relationship of 'Thresholds' between chemical mixtures and their respective component single chemicals was studied using three sets of data and two types of analyses. Two in vitro data sets involve cytotoxicity in human keratinocytes from treatment of metals and a metal mixture [Bae, D.S., Gennings, C., Carter, Jr., W.H., Yang, R.S.H., Campain, J.A., 2001. Toxicological interactions among arsenic, cadmium, chromium, and lead in human keratinocytes. Toxicol. Sci. 63, 132-142; Gennings, C., Carter, Jr., W.H., Campain, J.A., Bae, D.S., Yang, R.S.H., 2002. Statistical analysis of interactive cytotoxicity in human epidermal keratinocytes following exposure to a mixture of four metals. J.more » Agric. Biol. Environ. Stat. 7, 58-73], and induction of estrogen receptor alpha (ER-{alpha}) reporter gene in MCF-7 human breast cancer cells by estrogenic xenobiotics [Gennings, C., Carter, Jr., W.H., Carney, E.W., Charles, G.D., Gollapudi, B.B., Carchman, R.A., 2004. A novel flexible approach for evaluating fixed ratio mixtures of full and partial agonists. Toxicol. Sci. 80, 134-150]. The third data set came from PBPK modeling of gasoline and its components in the human. For in vitro cellular responses, we employed Benchmark Dose Software (BMDS) to obtain BMD{sub 01}, BMD{sub 05}, and BMD{sub 10}. We then plotted these BMDs against exposure concentrations for the chemical mixture and its components to assess the ranges and slopes of these BMD-concentration lines. In doing so, we consider certain BMDs to be 'Interaction Thresholds' or 'Thresholds' for mixtures and their component single chemicals and the slope of the line must be a reflection of the potency of the biological effects. For in vivo PBPK modeling, we used 0.1x TLVs, TLVs, and 10x TLVs for gasoline and six component markers as input dosing for PBPK modeling. In this case, the venous blood levels under the hypothetical exposure conditions become our designated 'Interaction Thresholds' or 'Thresholds' for gasoline and its component single chemicals. Our analyses revealed that the mixture 'Interaction Thresholds' appear to stay within the bounds of the 'Thresholds' of its respective component single chemicals. Although such a trend appears to be emerging, nevertheless, it should be emphasized that our analyses are based on limited data sets and further analyses on data sets, preferably the more comprehensive experimental data sets, are needed before a definitive conclusion can be drawn.« less

Enforcing positivity in intrusive PC-UQ methods for reactive ODE systems

DOE PAGES

Najm, Habib N.; Valorani, Mauro

2014-04-12

We explore the relation between the development of a non-negligible probability of negative states and the instability of numerical integration of the intrusive Galerkin ordinary differential equation system describing uncertain chemical ignition. To prevent this instability without resorting to either multi-element local polynomial chaos (PC) methods or increasing the order of the PC representation in time, we propose a procedure aimed at modifying the amplitude of the PC modes to bring the probability of negative state values below a user-defined threshold. This modification can be effectively described as a filtering procedure of the spectral PC coefficients, which is applied on-the-flymore » during the numerical integration when the current value of the probability of negative states exceeds the prescribed threshold. We demonstrate the filtering procedure using a simple model of an ignition process in a batch reactor. This is carried out by comparing different observables and error measures as obtained by non-intrusive Monte Carlo and Gauss-quadrature integration and the filtered intrusive procedure. Lastly, the filtering procedure has been shown to effectively stabilize divergent intrusive solutions, and also to improve the accuracy of stable intrusive solutions which are close to the stability limits.« less

A hybrid flower pollination algorithm based modified randomized location for multi-threshold medical image segmentation.

PubMed

Wang, Rui; Zhou, Yongquan; Zhao, Chengyan; Wu, Haizhou

2015-01-01

Multi-threshold image segmentation is a powerful image processing technique that is used for the preprocessing of pattern recognition and computer vision. However, traditional multilevel thresholding methods are computationally expensive because they involve exhaustively searching the optimal thresholds to optimize the objective functions. To overcome this drawback, this paper proposes a flower pollination algorithm with a randomized location modification. The proposed algorithm is used to find optimal threshold values for maximizing Otsu's objective functions with regard to eight medical grayscale images. When benchmarked against other state-of-the-art evolutionary algorithms, the new algorithm proves itself to be robust and effective through numerical experimental results including Otsu's objective values and standard deviations.

Thermal bistability-based method for real-time optimization of ultralow-threshold whispering gallery mode microlasers.

PubMed

Lin, Guoping; Candela, Y; Tillement, O; Cai, Zhiping; Lefèvre-Seguin, V; Hare, J

2012-12-15

A method based on thermal bistability for ultralow-threshold microlaser optimization is demonstrated. When sweeping the pump laser frequency across a pump resonance, the dynamic thermal bistability slows down the power variation. The resulting line shape modification enables a real-time monitoring of the laser characteristic. We demonstrate this method for a functionalized microsphere exhibiting a submicrowatt laser threshold. This approach is confirmed by comparing the results with a step-by-step recording in quasi-static thermal conditions.

77 FR 65506 - Airworthiness Directives; The Boeing Company Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-29

...We propose to supersede an existing airworthiness directive (AD) that applies to certain The Boeing Company Model 757-200 and - 200PF series airplanes. The existing AD currently requires modification of the nacelle strut and wing structure, and repair of any damage found during the modification. Since we issued that AD, a compliance time error involving the optional threshold formula was discovered, which could allow an airplane to exceed the acceptable compliance time for addressing the unsafe condition. This proposed AD would specify a maximum compliance time limit that overrides the optional threshold formula results. We are proposing this AD to prevent fatigue cracking in primary strut structure and consequent reduced structural integrity of the strut.

2004 Toxic Chemical Release Inventory Report for the Emergency Planning and Community Right-to-Know Act of 1986, Title III, Section 313

DOE Office of Scientific and Technical Information (OSTI.GOV)

M. Stockton

2006-01-15

Section 313 of Emergency Planning and Community Right-to-Know Act (EPCRA) specifically requires facilities to submit a Toxic Chemical Release Inventory Report (Form R) to the U.S. Environmental Protection Agency (EPA) and state agencies if the owners and operators manufacture, process, or otherwise use any of the listed toxic chemicals above listed threshold quantities. EPA compiles this data in the Toxic Release Inventory database. Form R reports for each chemical over threshold quantities must be submitted on or before July 1 each year and must cover activities that occurred at the facility during the previous year. For reporting year 2004, Losmore » Alamos National Laboratory (LANL or the Laboratory) submitted Form R reports for lead compounds, nitric acid, and nitrate compounds as required under the EPCRA Section 313. No other EPCRA Section 313 chemicals were used in 2004 above the reportable thresholds. This document provides a description of the evaluation of EPCRA Section 313 chemical use and threshold determinations for LANL for calendar year 2004, as well as background information about data included on the Form R reports.« less

Glycan Reader is improved to recognize most sugar types and chemical modifications in the Protein Data Bank.

PubMed

Park, Sang-Jun; Lee, Jumin; Patel, Dhilon S; Ma, Hongjing; Lee, Hui Sun; Jo, Sunhwan; Im, Wonpil

2017-10-01

Glycans play a central role in many essential biological processes. Glycan Reader was originally developed to simplify the reading of Protein Data Bank (PDB) files containing glycans through the automatic detection and annotation of sugars and glycosidic linkages between sugar units and to proteins, all based on atomic coordinates and connectivity information. Carbohydrates can have various chemical modifications at different positions, making their chemical space much diverse. Unfortunately, current PDB files do not provide exact annotations for most carbohydrate derivatives and more than 50% of PDB glycan chains have at least one carbohydrate derivative that could not be correctly recognized by the original Glycan Reader. Glycan Reader has been improved and now identifies most sugar types and chemical modifications (including various glycolipids) in the PDB, and both PDB and PDBx/mmCIF formats are supported. CHARMM-GUI Glycan Reader is updated to generate the simulation system and input of various glycoconjugates with most sugar types and chemical modifications. It also offers a new functionality to edit the glycan structures through addition/deletion/modification of glycosylation types, sugar types, chemical modifications, glycosidic linkages, and anomeric states. The simulation system and input files can be used for CHARMM, NAMD, GROMACS, AMBER, GENESIS, LAMMPS, Desmond, OpenMM, and CHARMM/OpenMM. Glycan Fragment Database in GlycanStructure.Org is also updated to provide an intuitive glycan sequence search tool for complex glycan structures with various chemical modifications in the PDB. http://www.charmm-gui.org/input/glycan and http://www.glycanstructure.org. wonpil@lehigh.edu. Supplementary data are available at Bioinformatics online. © The Author (2017). Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com

Constitutive Behavior and Modeling of Al-Cu Alloy Systems

DTIC Science & Technology

2013-05-01

Mechanical Threshold of Dynamically Deformed Copper and Nitronic 40 ." Journal de Physique, 1985: 25- 34. Gama, B. A., S. L. Lopatnikov, and J. W. G...38 3. MODIFIED ZERILLI-ARMSTRONG MODEL .................................... 40 3.1 Introduction... 40 3.2 Former Modifications to ZA Model by Zerilli and Armstrong .. 42 3.3 Modifications to ZA Model

Laser-induced Greenish-Blue Photoluminescence of Mesoporous Silicon Nanowires

PubMed Central

Choi, Yan-Ru; Zheng, Minrui; Bai, Fan; Liu, Junjun; Tok, Eng-Soon; Huang, Zhifeng; Sow, Chorng-Haur

2014-01-01

Solid silicon nanowires and their luminescent properties have been widely studied, but lesser is known about the optical properties of mesoporous silicon nanowires (mp-SiNWs). In this work, we present a facile method to generate greenish-blue photoluminescence (GB-PL) by fast scanning a focused green laser beam (wavelength of 532 nm) on a close-packed array of mp-SiNWs to carry out photo-induced chemical modification. The threshold of laser power is 5 mW to excite the GB-PL, whose intensity increases with laser power in the range of 5–105 mW. The quenching of GB-PL comes to occur beyond 105 mW. The in-vacuum annealing effectively excites the GB-PL in the pristine mp-SiNWs and enhances the GB-PL of the laser-modified mp-SiNWs. A complex model of the laser-induced surface modification is proposed to account for the laser-power and post-annealing effect. Moreover, the fast scanning of focused laser beam enables us to locally tailor mp-SiNWs en route to a wide variety of micropatterns with different optical functionality, and we demonstrate the feasibility in the application of creating hidden images. PMID:24820533

Heterosynaptic metaplasticity in the hippocampus in vivo: A BCM-like modifiable threshold for LTP

PubMed Central

Abraham, Wickliffe C.; Mason-Parker, Sara E.; Bear, Mark F.; Webb, Sarah; Tate, Warren P.

2001-01-01

The homeostatic maintenance of the “modification threshold” for inducing long-term potentiation (LTP) is a fundamental feature of the Bienenstock, Cooper, and Munro (BCM) model of synaptic plasticity. In the present study, two key features of the modification threshold, its heterosynaptic expression and its regulation by postsynaptic neural activity, were tested experimentally in the dentate gyrus of awake, freely moving rats. Conditioning stimulation ranging from 10 to 1,440 brief 400-Hz trains, when applied to medial perforant path afferents, raised the threshold for LTP induction heterosynaptically in the neighboring lateral perforant path synapses. This effect recovered slowly over a 7- to 35-day period. The same conditioning paradigms, however, did not affect the reversal of long-term depression. The inhibition of LTP by medial-path conditioning stimulation was N-methyl-D-aspartate (NMDA) receptor-dependent, but antidromic stimulation of the granule cells could also inhibit lateral path LTP induction, independently of NMDA receptor activation. Increased calcium buffering is a potential mechanism underlying the altered LTP threshold, but the levels of two important calcium-binding proteins did not increase after conditioning stimulation, nor was de novo protein synthesis required for generating the threshold shift. These data confirm, in an in vivo model, two key postulates of the BCM model regarding the LTP threshold. They also provide further evidence for the broad sensitivity of synaptic plasticity mechanisms to the history of prior activity, i.e., metaplasticity. PMID:11517323

Dependence of interface charge trapping on channel engineering in pentacene field effect transistors.

PubMed

Lee, Sunwoo; Park, Junghyuck; Park, In-Sung; Ahn, Jinho

2014-07-01

We investigate the dependence of charge carrier mobility by trap states at various interface regions through channel engineering. Prior to evaluation of interface trap density, the electrical performance in pentaene field effect transistors (FET) with high-k gate oxide are also investigated depending on four channel engineering. As a channel engineering, gas treatment, coatings of thin polymer layer, and chemical surface modification using small molecules were carried out. After channel engineering, the performance of device as well as interface trap density calculated by conductance method are remarkably improved. It is found that the reduced interface trap density is closely related to decreasing the sub-threshold swing and improving the mobility. Particularly, we also found that performance of device such as mobility, subthreshold swing, and interface trap density after gas same is comparable to those of OTS.

Photo-Double Ionization: Threshold Law and Low-Energy Behavior

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Temkin, A.

2007-01-01

The threshold law for photoejection of two electrons from atoms (PDI) is derived from a modification of the Coulomb-dipole (C-D) theory. The C-D theory applies to two-electron ejection from negative ions (photo-double detachment:PDD). The modification consists of correctly accounting for the fact that in PDI that the two escaping electrons see a Coulomb field, asymptotically no matter what their relative distances from the residual ion are. We find in the contralinear spherically symmetric model that the analytic threshold law Q(E), i.e. the yield of residual ions, to be Q Integral of (E) varies as E + (C(sub w) E(sup gamma W)) +CE(sup 5/4) sin [1/2 ln E + phi]/ln(E). The first and third terms are beyond the Wannier law. Our threshold law can only be rigorously justified for residual energies <= 10(exp -3) eV. Nevertheless in the present experimental range (0.1 - 4 eV), the form, even without the second term, can be fitted to experimental results of PDI for He, Li, and Be, in contrast to the Wannier law which has a larger deviation from the data for Li and Be.

Application of Key Events and Analysis to Chemical Carcinogens and Noncarcinogens

EPA Science Inventory

The existence of thresholds for toxicants is a matter of debate in chemical rsk assessment and regulation. Current risk assessment methods are based on the assumption that, in the basense of sufficient data, carcinogenesis does not have a threshold, while non-carcinogenic endpoi...

Nonmonotonic Dose-Response Curves and Endocrine-Disrupting Chemicals: Fact or Falderal?**

EPA Science Inventory

Nonmonotonic Dose-Response Curves and Endocrine-Disrupting Chemicals: Fact or Falderal? The shape of the dose response curve in the low dose region has been debated since the 1940s, originally focusing on linear no threshold (LNT) versus threshold responses for cancer and noncanc...

Detecting Chemically Modified DNA Bases Using Surface Enhanced Raman Spectroscopy

PubMed Central

Barhoumi, Aoune; Halas, Naomi J.

2013-01-01

Post-translational modifications of DNA- changes in the chemical structure of individual bases that occur without changes in the DNA sequence- are known to alter gene expression. They are believed to result in frequently deleterious phenotypic changes, such as cancer. Methylation of adenine, methylation and hydroxymethylation of cytosine, and guanine oxidation are the primary DNA base modifications identified to date. Here we show it is possible to use surface enhanced Raman spectroscopy (SERS) to detect these primary DNA base modifications. SERS detection of modified DNA bases is label-free and requires minimal additional sample preparation, reducing the possibility of additional chemical modifications induced prior to measurement. This approach shows the feasibility of DNA base modification assessment as a potentially routine analysis that may be further developed for clinical diagnostics. PMID:24427449

Detecting Chemically Modified DNA Bases Using Surface Enhanced Raman Spectroscopy.

PubMed

Barhoumi, Aoune; Halas, Naomi J

2011-12-15

Post-translational modifications of DNA- changes in the chemical structure of individual bases that occur without changes in the DNA sequence- are known to alter gene expression. They are believed to result in frequently deleterious phenotypic changes, such as cancer. Methylation of adenine, methylation and hydroxymethylation of cytosine, and guanine oxidation are the primary DNA base modifications identified to date. Here we show it is possible to use surface enhanced Raman spectroscopy (SERS) to detect these primary DNA base modifications. SERS detection of modified DNA bases is label-free and requires minimal additional sample preparation, reducing the possibility of additional chemical modifications induced prior to measurement. This approach shows the feasibility of DNA base modification assessment as a potentially routine analysis that may be further developed for clinical diagnostics.

40 CFR 68.115 - Threshold determination.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Threshold determination. 68.115 Section 68.115 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CHEMICAL ACCIDENT PREVENTION PROVISIONS Regulated Substances for Accidental Release Prevention § 68.115 Threshold determination. (a) A threshold...

40 CFR 68.115 - Threshold determination.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Threshold determination. 68.115 Section 68.115 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CHEMICAL ACCIDENT PREVENTION PROVISIONS Regulated Substances for Accidental Release Prevention § 68.115 Threshold determination. (a) A threshold...

40 CFR 68.115 - Threshold determination.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Threshold determination. 68.115 Section 68.115 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CHEMICAL ACCIDENT PREVENTION PROVISIONS Regulated Substances for Accidental Release Prevention § 68.115 Threshold determination. (a) A threshold...

40 CFR 68.115 - Threshold determination.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Threshold determination. 68.115 Section 68.115 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CHEMICAL ACCIDENT PREVENTION PROVISIONS Regulated Substances for Accidental Release Prevention § 68.115 Threshold determination. (a) A threshold...

Modification degrees at specific sites on heparan sulphate: an approach to measure chemical modifications on biological molecules with stable isotope labelling

PubMed Central

Wu, Zhengliang L.; Lech, Miroslaw

2005-01-01

Chemical modification of biological molecules is a general mechanism for cellular regulation. A quantitative approach has been developed to measure the extent of modification on HS (heparan sulphates). Sulphation on HS by sulphotransferases leads to variable sulphation levels, which allows cells to tune their affinities to various extracellular proteins, including growth factors. With stable isotope labelling and HPLC-coupled MS, modification degrees at various O-sulphation sites could be determined. A bovine kidney HS sample was first saturated in vitro with 34S by an OST (O-sulphotransferase), then digested with nitrous acid and analysed with HPLC-coupled MS. The 34S-labelled oligosaccharides were identified based on their unique isotope clusters. The modification degrees at the sulphotransferase recognition sites were obtained by calculating the intensities of isotopic peaks in the isotope clusters. The modification degrees at 3-OST-1 and 6-OST-1 sites were examined in detail. This approach can also be used to study other types of chemical modifications on biological molecules. PMID:15743272

40 CFR 455.47 - Pretreatment standards for new sources (PSNS).

Code of Federal Regulations, 2012 CFR

2012-07-01

...) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) PESTICIDE CHEMICALS Pesticide Chemicals Formulating and... received a modification by Best Engineering Judgement for modifications not listed in Table 8 to this part...

40 CFR 455.47 - Pretreatment standards for new sources (PSNS).

Code of Federal Regulations, 2014 CFR

2014-07-01

...) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) PESTICIDE CHEMICALS Pesticide Chemicals Formulating and... received a modification by Best Engineering Judgement for modifications not listed in Table 8 to this part...

Threshold and non-threshold chemical carcinogens: A survey of the present regulatory landscape.

PubMed

Bevan, Ruth J; Harrison, Paul T C

2017-08-01

For the proper regulation of a carcinogenic material it is necessary to fully understand its mode of action, and in particular whether it demonstrates a threshold of effect. This paper explores our present understanding of carcinogenicity and the mechanisms underlying the carcinogenic response. The concepts of genotoxic and non-genotoxic and threshold and non-threshold carcinogens are fully described. We provide summary tables of the types of cancer considered to be associated with exposure to a number of carcinogens and the available evidence relating to whether carcinogenicity occurs through a threshold or non-threshold mechanism. In light of these observations we consider how different regulatory bodies approach the question of chemical carcinogenesis, looking in particular at the definitions and methodologies used to derive Occupational Exposure Levels (OELs) for carcinogens. We conclude that unless proper differentiation is made between threshold and non-threshold carcinogens, inappropriate risk management measures may be put in place - and lead also to difficulties in translating carcinogenicity research findings into appropriate health policies. We recommend that clear differentiation between threshold and non-threshold carcinogens should be made by all expert groups and regulatory bodies dealing with carcinogen classification and risk assessment. Copyright © 2017 Elsevier Inc. All rights reserved.

40 CFR 180.2010 - Threshold of regulation determinations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Threshold of regulation determinations. 180.2010 Section 180.2010 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Pesticide Chemicals Not Requiring a Tolerance or an Exemption From...

40 CFR 180.2010 - Threshold of regulation determinations.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Threshold of regulation determinations. 180.2010 Section 180.2010 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Pesticide Chemicals Not Requiring a Tolerance or an Exemption From...

40 CFR 180.2010 - Threshold of regulation determinations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Threshold of regulation determinations... Requiring a Tolerance or an Exemption From a Tolerance § 180.2010 Threshold of regulation determinations... on EPA's determination that the uses are below the threshold of regulation. Pesticide Chemical CAS...

40 CFR 180.2010 - Threshold of regulation determinations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Threshold of regulation determinations... Requiring a Tolerance or an Exemption From a Tolerance § 180.2010 Threshold of regulation determinations... on EPA's determination that the uses are below the threshold of regulation. Pesticide Chemical CAS...

40 CFR 180.2010 - Threshold of regulation determinations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Threshold of regulation determinations... Requiring a Tolerance or an Exemption From a Tolerance § 180.2010 Threshold of regulation determinations... on EPA's determination that the uses are below the threshold of regulation. Pesticide Chemical CAS...

Posttranscriptional RNA Modifications: playing metabolic games in a cell's chemical Legoland.

PubMed

Helm, Mark; Alfonzo, Juan D

2014-02-20

Nature combines existing biochemical building blocks, at times with subtlety of purpose. RNA modifications are a prime example of this, where standard RNA nucleosides are decorated with chemical groups and building blocks that we recall from our basic biochemistry lectures. The result: a wealth of chemical diversity whose full biological relevance has remained elusive despite being public knowledge for some time. Here, we highlight several modifications that, because of their chemical intricacy, rely on seemingly unrelated pathways to provide cofactors for their synthesis. Besides their immediate role in affecting RNA function, modifications may act as sensors and transducers of information that connect a cell's metabolic state to its translational output, carefully orchestrating a delicate balance between metabolic rate and protein synthesis at a system's level. Copyright © 2014 Elsevier Ltd. All rights reserved.

Testing a Threshold-Based Bed Bug Management Approach in Apartment Buildings.

PubMed

Singh, Narinderpal; Wang, Changlu; Zha, Chen; Cooper, Richard; Robson, Mark

2017-07-26

We tested a threshold-based bed bug ( Cimex lectularius L.) management approach with the goal of achieving elimination with minimal or no insecticide application. Thirty-two bed bug infested apartments were identified. These apartments were divided into four treatment groups based on apartment size and initial bed bug count, obtained through a combination of visual inspection and bed bug monitors: I- Non-chemical only in apartments with 1-12 bed bug count, II- Chemical control only in apartments with 1-12 bed bug count, III- Non-chemical and chemical control in apartments with >12 bed bug count, and IV- Chemical control only in apartments with ≥11 bed bug count. All apartments were monitored or treated once every two weeks for a maximum of 28 wk. Treatment I eliminated bed bugs in a similar amount of time to treatment II. Time to eliminate bed bugs was similar between treatment III and IV but required significantly less insecticide spray in treatment III than that in treatment IV. A threshold-based management approach (non-chemical only or non-chemical and chemical) can eliminate bed bugs in a similar amount of time, using little to no pesticide compared to a chemical only approach.

Testing a Threshold-Based Bed Bug Management Approach in Apartment Buildings

PubMed Central

Singh, Narinderpal; Zha, Chen; Cooper, Richard; Robson, Mark

2017-01-01

We tested a threshold-based bed bug (Cimex lectularius L.) management approach with the goal of achieving elimination with minimal or no insecticide application. Thirty-two bed bug infested apartments were identified. These apartments were divided into four treatment groups based on apartment size and initial bed bug count, obtained through a combination of visual inspection and bed bug monitors: I- Non-chemical only in apartments with 1–12 bed bug count, II- Chemical control only in apartments with 1–12 bed bug count, III- Non-chemical and chemical control in apartments with >12 bed bug count, and IV- Chemical control only in apartments with ≥11 bed bug count. All apartments were monitored or treated once every two weeks for a maximum of 28 wk. Treatment I eliminated bed bugs in a similar amount of time to treatment II. Time to eliminate bed bugs was similar between treatment III and IV but required significantly less insecticide spray in treatment III than that in treatment IV. A threshold-based management approach (non-chemical only or non-chemical and chemical) can eliminate bed bugs in a similar amount of time, using little to no pesticide compared to a chemical only approach. PMID:28933720

Refinement of a thermal threshold probe to prevent burns.

PubMed

Dixon, M J; Taylor, P M; Slingsby, L C; Murrell, J C

2016-02-01

Thermal threshold testing is commonly used for pain research. The stimulus may cause burning and merits prevention. Thermal probe modifications hypothesized to reduce burning were evaluated for practicality and effect. Studies were conducted on two humans and eight cats. Unmodified probe 0 was tested on two humans and promising modifications were also evaluated on cats. Probe 1 incorporated rapid cooling after threshold was reached: probe 1a used a Peltier system and probe 1b used water cooling. Probe 2 released skin contact immediately after threshold. Probe 3 (developed in the light of evidence of 'hot spots' in probe 0) incorporated reduced thermal mass and even heating across the skin contact area. Human skin was heated to 48℃ (6℃ above threshold) and the resulting burn was evaluated using area of injury and a simple descriptive scale (SDS). Probe 1a cooled the skin but required further heat dissipation, excessive power, was not 'fail-safe' and was inappropriate for animal mounting. Probe 1b caused less damage than no cooling (27 ± 13 and 38 ± 11 mm(2) respectively, P = 0.0266; median SDS 1.5 and 4 respectively, P = 0.0317) but was cumbersome. Probe 2 was unwieldy and was not evaluated further. Probe 3 produced even heating without blistering in humans. With probe 3 in cats, after opioid treatment, thermal threshold reached cut-out (55℃) on 24 occasions, exceeded 50℃ in a further 32 tests and exceeded 48℃ in the remainder. No skin damage was evident immediately after testing and mild hyperaemia in three cats at 2-3 days resolved rapidly. Probe 3 appeared to be suitable for thermal threshold testing. © The Author(s) 2015.

40 CFR 372.27 - Alternate threshold and certification.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 29 2013-07-01 2013-07-01 false Alternate threshold and certification...-TO-KNOW Reporting Requirements § 372.27 Alternate threshold and certification. (a) Except as provided... toxic chemical, the owner or operator of a facility may apply an alternate threshold of 1 million pounds...

Physical and chemical modification of starches: A review.

PubMed

Zia-Ud-Din; Xiong, Hanguo; Fei, Peng

2017-08-13

The development of green material in the last decade has been increased, which tends to reduce the impact of humans on the environment. Starch as an agro-sourced polymer has become very popular recently due to its characteristics, such as wide availability, low cost, and total compostability without toxic residues. Starch is the most abundant organic compound found in nature after cellulose. Starches are inherently unsuitable for most applications and, therefore, must be modified physically and/or chemically to enhance their positive attributes and/or to minimize their defects. Modification of starches is generally carried out by using physical methods that are simple and inexpensive due to the absence of chemical agents. However, chemical modification involves the exploitation of hydroxyl group present in the starches that brings about the desired results for the utilization of starches for specific applications. All these techniques have the tendency to produce starches with altered physicochemical properties and modified structural attributes for various food and nonfood applications. This paper reviews the recent knowledge and developments using physical modification methods, some chemical modification methods, and a combination of both to produce a novel molecule with substantial applications, in food industry along with future perspectives.

Proteomic analyses of the environmental toxicity of carcinogenic chemicals

EPA Science Inventory

Protein expression and posttranslational modifications consistently change in response to the exposure to environmental chemicals. Recent technological advances in proteomics provide new tools for more efficient characterization of protein expression and posttranslational modific...

Tungsten oxide thin film exposed to low energy D and He plasma: evidence for a thermal enhancement of the erosion yield

NASA Astrophysics Data System (ADS)

Hijazi, Hussein; Martin, C.; Roubin, P.; Addab, Y.; Cabie, C.; Pardanaud, C.; Bannister, M.; Meyer, F.

2017-10-01

Nanocrystalline tungsten oxide thin films (25 nm - 250 nm thickness) produced by thermal oxidation of a tungsten substrate were exposed to low energy D and He plasma. Low energy D plasma exposure (11 eV/D+) of these films have resulted in the formation of a tungsten bronze (DxWO3) clearly observed by Raman microscopy. D plasma bombardment (4 1021 m-2) has also induced a color change of the oxide layer which is similar to the well-known electro-chromic effect and has been named ``plasma-chromic effect''. To unravel physical and chemical origins of the modifications observed under exposure, similar tungsten oxide films were also exposed to low energy helium plasma (20 eV/He+) . Due to the low fluence (4 1021 m-2) and low ion energy (20 eV), at room temperature, He exposure has induced only very few morphological and structural modifications. On the contrary, at 673 K, significant erosion is observed, which gives evidence for an unexpected thermal enhancement of the erosion yield. We present here new results concerning He beam exposures at low fluence (4 1021 m-2) varying the He+ energy from 20 eV to 320 eV to measure the tungsten oxide sputtering threshold energy. Detailed analyses before/after exposure to describe the D and He interaction with the oxide layer, its erosion and structural modification at the atomic and micrometer scale will be presented.

Mechanisms of breathing instability in patients with obstructive sleep apnea.

PubMed

Younes, Magdy; Ostrowski, Michele; Atkar, Raj; Laprairie, John; Siemens, Andrea; Hanly, Patrick

2007-12-01

The response to chemical stimuli (chemical responsiveness) and the increases in respiratory drive required for arousal (arousal threshold) and for opening the airway without arousal (effective recruitment threshold) are important determinants of ventilatory instability and, hence, severity of obstructive apnea. We measured these variables in 21 obstructive apnea patients (apnea-hypopnea index 91 +/- 24 h(-1)) while on continuous-positive-airway pressure. During sleep, pressure was intermittently reduced (dial down) to induce severe hypopneas. Dial downs were done on room air and following approximately 30 s of breathing hypercapneic and/or hypoxic mixtures, which induced a range of ventilatory stimulation before dial down. Ventilation just before dial down and flow during dial down were measured. Chemical responsiveness, estimated as the percent increase in ventilation during the 5(th) breath following administration of 6% CO(2) combined with approximately 4% desaturation, was large (187 +/- 117%). Arousal threshold, estimated as the percent increase in ventilation associated with a 50% probability of arousal, ranged from 40% to >268% and was <120% in 12/21 patients, indicating that in many patients arousal occurs with modest changes in chemical drive. Effective recruitment threshold, estimated as percent increase in pre-dial-down ventilation associated with a significant increase in dial-down flow, ranged from zero to >174% and was <110% in 12/21 patients, indicating that in many patients reflex dilatation occurs with modest increases in drive. The two thresholds were not correlated. In most OSA patients, airway patency may be maintained with only modest increases in chemical drive, but instability results because of a low arousal threshold and a brisk increase in drive following brief reduction in alveolar ventilation.

siRNAmod: A database of experimentally validated chemically modified siRNAs.

PubMed

Dar, Showkat Ahmad; Thakur, Anamika; Qureshi, Abid; Kumar, Manoj

2016-01-28

Small interfering RNA (siRNA) technology has vast potential for functional genomics and development of therapeutics. However, it faces many obstacles predominantly instability of siRNAs due to nuclease digestion and subsequently biologically short half-life. Chemical modifications in siRNAs provide means to overcome these shortcomings and improve their stability and potency. Despite enormous utility bioinformatics resource of these chemically modified siRNAs (cm-siRNAs) is lacking. Therefore, we have developed siRNAmod, a specialized databank for chemically modified siRNAs. Currently, our repository contains a total of 4894 chemically modified-siRNA sequences, comprising 128 unique chemical modifications on different positions with various permutations and combinations. It incorporates important information on siRNA sequence, chemical modification, their number and respective position, structure, simplified molecular input line entry system canonical (SMILES), efficacy of modified siRNA, target gene, cell line, experimental methods, reference etc. It is developed and hosted using Linux Apache MySQL PHP (LAMP) software bundle. Standard user-friendly browse, search facility and analysis tools are also integrated. It would assist in understanding the effect of chemical modifications and further development of stable and efficacious siRNAs for research as well as therapeutics. siRNAmod is freely available at: http://crdd.osdd.net/servers/sirnamod.

Chemical Modification of Boron-Doped Diamond Electrodes for Applications to Biosensors and Biosensing.

PubMed

Svítková, Jana; Ignat, Teodora; Švorc, Ľubomír; Labuda, Ján; Barek, Jiří

2016-05-03

Boron-doped diamond (BDD) is a prospective electrode material that possesses many exceptional properties including wide potential window, low noise, low and stable background current, chemical and mechanical stability, good biocompatibility, and last but not least exceptional resistance to passivation. These characteristics extend its usability in various areas of electrochemistry as evidenced by increasing number of published articles over the past two decades. The idea of chemically modifying BDD electrodes with molecular species attached to the surface for the purpose of creating a rational design has found promising applications in the past few years. BDD electrodes have appeared to be excellent substrate materials for various chemical modifications and subsequent application to biosensors and biosensing. Hence, this article presents modification strategies that have extended applications of BDD electrodes in electroanalytical chemistry. Different methods and steps of surface modification of this electrode material for biosensing and construction of biosensors are discussed.

Performance of new thresholds of the Glasgow Blatchford score in managing patients with upper gastrointestinal bleeding.

PubMed

Laursen, Stig B; Dalton, Harry R; Murray, Iain A; Michell, Nick; Johnston, Matt R; Schultz, Michael; Hansen, Jane M; Schaffalitzky de Muckadell, Ove B; Blatchford, Oliver; Stanley, Adrian J

2015-01-01

Upper gastrointestinal hemorrhage (UGIH) is a common cause of hospital admission. The Glasgow Blatchford score (GBS) is an accurate determinant of patients' risk for hospital-based intervention or death. Patients with a GBS of 0 are at low risk for poor outcome and could be managed as outpatients. Some investigators therefore have proposed extending the definition of low-risk patients by using a higher GBS cut-off value, possibly with an age adjustment. We compared 3 thresholds of the GBS and 2 age-adjusted modifications to identify the optimal cut-off value or modification. We performed an observational study of 2305 consecutive patients presenting with UGIH at 4 centers (Scotland, England, Denmark, and New Zealand). The performance of each threshold and modification was evaluated based on sensitivity and specificity analyses, the proportion of low-risk patients identified, and outcomes of patients classified as low risk. There were differences in age (P = .0001), need for intervention (P < .0001), mortality (P < .015), and GBS (P = .0001) among sites. All systems identified low-risk patients with high levels of sensitivity (>97%). The GBS at cut-off values of ≤1 and ≤2, and both modifications, identified low-risk patients with higher levels of specificity (40%-49%) than the GBS with a cut-off value of 0 (22% specificity; P < .001). The GBS at a cut-off value of ≤2 had the highest specificity, but 3% of patients classified as low-risk patients had adverse outcomes. All GBS cut-off values, and score modifications, had low levels of specificity when tested in New Zealand (2.5%-11%). A GBS cut-off value of ≤1 and both GBS modifications identify almost twice as many low-risk patients with UGIH as a GBS at a cut-off value of 0. Implementing a protocol for outpatient management, based on one of these scores, could reduce hospital admissions by 15% to 20%. Copyright © 2015 AGA Institute. Published by Elsevier Inc. All rights reserved.

Chemical modification of wood : a short review

Treesearch

Roger M. Rowell

2006-01-01

For most markets for wood, it is used without any treatments or modifications. When wood is used in adverse environments, it may be treated with chemicals to help prevent decay, improve water resistance, reduce the effects of ultraviolet radiation or increase fire retardancy. Many of these treatments involve the use of toxic or corrosive chemicals that can harm the...

40 CFR Appendix A to Part 355 - The List of Extremely Hazardous Substances and Their Threshold Planning Quantities

Code of Federal Regulations, 2013 CFR

2013-07-01

... Substances and Their Threshold Planning Quantities A Appendix A to Part 355 Protection of Environment... Substances and Their Threshold Planning Quantities [Alphabetical Order] CAS No. Chemical name Notes Reportable quantity *(pounds) Threshold planning quantity(pounds) 75-86-5 Acetone Cyanohydrin 10 1,000 1752...

Minimal 2'-O-methyl phosphorothioate linkage modification pattern of synthetic guide RNAs for increased stability and efficient CRISPR-Cas9 gene editing avoiding cellular toxicity

PubMed Central

Basila, Megan; Kelley, Melissa L.

2017-01-01

Since its initial application in mammalian cells, CRISPR-Cas9 has rapidly become a preferred method for genome engineering experiments. The Cas9 nuclease is targeted to genomic DNA using guide RNAs (gRNA), either as the native dual RNA system consisting of a DNA-targeting CRISPR RNA (crRNA) and a trans-activating crRNA (tracrRNA), or as a chimeric single guide RNA (sgRNA). Entirely DNA-free CRISPR-Cas9 systems using either Cas9 protein or Cas9 mRNA and chemically synthesized gRNAs allow for transient expression of CRISPR-Cas9 components, thereby reducing the potential for off-targeting, which is a significant advantage in therapeutic applications. In addition, the use of synthetic gRNA allows for the incorporation of chemical modifications for enhanced properties including improved stability. Previous studies have demonstrated the utility of chemically modified gRNAs, but have focused on one pattern with multiple modifications in co-electroporation with Cas9 mRNA or multiple modifications and patterns with Cas9 plasmid lipid co-transfections. Here we present gene editing results using a series of chemically modified synthetic sgRNA molecules and chemically modified crRNA:tracrRNA molecules in both electroporation and lipid transfection assessing indel formation and/or phenotypic gene knockout. We show that while modifications are required for co-electroporation with Cas9 mRNA, some modification patterns of the gRNA are toxic to cells compared to the unmodified gRNA and most modification patterns do not significantly improve gene editing efficiency. We also present modification patterns of the gRNA that can modestly improve Cas9 gene editing efficiency when co-transfected with Cas9 mRNA or Cas9 protein (> 1.5-fold difference). These results indicate that for certain applications, including those relevant to primary cells, the incorporation of some, but not all chemical modification patterns on synthetic crRNA:tracrRNA or sgRNA can be beneficial to CRISPR-Cas9 gene editing. PMID:29176845

Minimal 2'-O-methyl phosphorothioate linkage modification pattern of synthetic guide RNAs for increased stability and efficient CRISPR-Cas9 gene editing avoiding cellular toxicity.

PubMed

Basila, Megan; Kelley, Melissa L; Smith, Anja van Brabant

2017-01-01

Since its initial application in mammalian cells, CRISPR-Cas9 has rapidly become a preferred method for genome engineering experiments. The Cas9 nuclease is targeted to genomic DNA using guide RNAs (gRNA), either as the native dual RNA system consisting of a DNA-targeting CRISPR RNA (crRNA) and a trans-activating crRNA (tracrRNA), or as a chimeric single guide RNA (sgRNA). Entirely DNA-free CRISPR-Cas9 systems using either Cas9 protein or Cas9 mRNA and chemically synthesized gRNAs allow for transient expression of CRISPR-Cas9 components, thereby reducing the potential for off-targeting, which is a significant advantage in therapeutic applications. In addition, the use of synthetic gRNA allows for the incorporation of chemical modifications for enhanced properties including improved stability. Previous studies have demonstrated the utility of chemically modified gRNAs, but have focused on one pattern with multiple modifications in co-electroporation with Cas9 mRNA or multiple modifications and patterns with Cas9 plasmid lipid co-transfections. Here we present gene editing results using a series of chemically modified synthetic sgRNA molecules and chemically modified crRNA:tracrRNA molecules in both electroporation and lipid transfection assessing indel formation and/or phenotypic gene knockout. We show that while modifications are required for co-electroporation with Cas9 mRNA, some modification patterns of the gRNA are toxic to cells compared to the unmodified gRNA and most modification patterns do not significantly improve gene editing efficiency. We also present modification patterns of the gRNA that can modestly improve Cas9 gene editing efficiency when co-transfected with Cas9 mRNA or Cas9 protein (> 1.5-fold difference). These results indicate that for certain applications, including those relevant to primary cells, the incorporation of some, but not all chemical modification patterns on synthetic crRNA:tracrRNA or sgRNA can be beneficial to CRISPR-Cas9 gene editing.

76 FR 65769 - Airport Improvement Program: Modifications to Benefit Cost Analysis (BCA) Threshold

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-24

...This document announces the publication of the final policy changes to the Federal Aviation Administration's policy requiring a benefit cost analysis (BCA) for capacity projects funded by Airport Improvement Program (AIP) discretionary funds. On December 16, 2010, the FAA issued a Notice of Availability of Draft Guidance and Request for Comments with regard to the modification of its policy requiring benefit cost analyses (BCA) for capacity projects, which was published in the Federal Register. (78 FR 78798-02, December 16, 2010). The FAA now is (1) Issuing the final policy modifying the threshold at which BCAs are required from $5 million to $10 million in Airport Improvement Program (AIP) Discretionary funds, and (2) responding to comments requested in the Notice on December 16, 2010.

An Unorthodox Sensory Adaptation Site in the Escherichia coli Serine Chemoreceptor

PubMed Central

Han, Xue-Sheng

2014-01-01

The serine chemoreceptor of Escherichia coli contains four canonical methylation sites for sensory adaptation that lie near intersubunit helix interfaces of the Tsr homodimer. An unexplored fifth methylation site, E502, lies at an intrasubunit helix interface closest to the HAMP domain that controls input-output signaling in methyl-accepting chemotaxis proteins. We analyzed, with in vivo Förster resonance energy transfer (FRET) kinase assays, the serine thresholds and response cooperativities of Tsr receptors with different mutationally imposed modifications at sites 1 to 4 and/or at site 5. Tsr variants carrying E or Q at residue 502, in combination with unmodifiable D and N replacements at adaptation sites 1 to 4, underwent both methylation and demethylation/deamidation, although detection of the latter modifications required elevated intracellular levels of CheB. These Tsr variants could not mediate a chemotactic response to serine spatial gradients, demonstrating that adaptational modifications at E502 alone are not sufficient for Tsr function. Moreover, E502 is not critical for Tsr function, because only two amino acid replacements at this residue abrogated serine chemotaxis: Tsr-E502P had extreme kinase-off output and Tsr-E502I had extreme kinase-on output. These large threshold shifts are probably due to the unique HAMP-proximal location of methylation site 5. However, a methylation-mimicking glutamine at any Tsr modification site raised the serine response threshold, suggesting that all sites influence signaling by the same general mechanism, presumably through changes in packing stability of the methylation helix bundle. These findings are consistent with control of input-output signaling in Tsr through dynamic interplay of the structural stabilities of the HAMP and methylation bundles. PMID:24272777

Photo-Double Ionization: Threshold Law and Low-Energy Behavior

NASA Technical Reports Server (NTRS)

Bhatia, Anand

2008-01-01

The threshold law for photoejection of two electrons from atoms (PDI) is derived from a modification of the Coulomb-dipole (C-D) theory. The C-D theory applies to two-electron ejection from negative ions (photo-double detachment:PDD). The modification consists of correctly accounting for the fact that in PDI that the two escaping electrons see a Coulomb field, asymptotically no matter what their relative distances from the residual ion are. We find in the contralinear spherically symmetric model that the analytic threshold law Q(E),i. e. the yield of residual ions, to be Qf(E)approaches E + CwE(sup gamma(w)) + CE(sup 5/4)sin[1/2 ln(E + theta)]/ln(E). The first and third terms are beyond the Wannier law. Our threshold law can only be rigorously justified for residual energies less than or equal to 10(exp -3) eV. Nevertheless in the present experimental range (0.1 - 4 eV), the form, even without the second term, can be fitted to experimental results of PDI for He, Li, and Be, in contrast to the Wannier law which has a larger deviation from the data for Li and Be, for both of which the data show signs of modulation.

Can the human lumbar posterior columns be stimulated by transcutaneous spinal cord stimulation? A modeling study

PubMed Central

Danner, Simon M.; Hofstoetter, Ursula S.; Ladenbauer, Josef; Rattay, Frank; Minassian, Karen

2014-01-01

Stimulation of different spinal cord segments in humans is a widely developed clinical practice for modification of pain, altered sensation and movement. The human lumbar cord has become a target for modification of motor control by epidural and more recently by transcutaneous spinal cord stimulation. Posterior columns of the lumbar spinal cord represent a vertical system of axons and when activated can add other inputs to the motor control of the spinal cord than stimulated posterior roots. We used a detailed three-dimensional volume conductor model of the torso and the McIntyre-Richard-Grill axon model to calculate the thresholds of axons within the posterior columns in response to transcutaneous lumbar spinal cord stimulation. Superficially located large diameter posterior column fibers with multiple collaterals have a threshold of 45.4 V, three times higher than posterior root fibers (14.1 V). With the stimulation strength needed to activate posterior column axons, posterior root fibers of large and small diameters as well as anterior root fibers are co-activated. The reported results inform on these threshold differences, when stimulation is applied to the posterior structures of the lumbar cord at intensities above the threshold of large-diameter posterior root fibers. PMID:21401670

The theory of ionospheric focused heating

NASA Technical Reports Server (NTRS)

Bernhardt, P. A.; Duncan, L. M.

1987-01-01

Ionospheric modification by high power radio waves and by chemical releases are combined in a theoretical study of ionospheric focused heating. The release of materials which promote electron-ion recombination creates a hole in the bottomside ionosphere. The ionospheric hole focuses high power radio waves from a ground-based transmitter to give a 20 dB or greater enhancement in power density. The intense radio beam excites atomic oxygen by collisions with accelerated electrons. Airglow from the excited oxygen provides a visible trace of the focused beam. The large increase in the intensity of the radio beam stimulates new wave-plasma interactions. Numerical simulations show that the threshold for the two-plasmon decay instability is exceeded. The interaction of the pump electromagnetic wave with the backward plasmon produces a scattered electromagnetic wave at 3/2 the pump frequency. The scattered wave provides a unique signature of the two-plasmon decay process for ground-based detection.

Enhanced translocation of single DNA molecules through α-hemolysin nanopores by manipulation of internal charge

PubMed Central

Maglia, Giovanni; Restrepo, Marcela Rincon; Mikhailova, Ellina; Bayley, Hagan

2008-01-01

Both protein and solid-state nanopores are under intense investigation for the analysis of nucleic acids. A crucial advantage of protein nanopores is that site-directed mutagenesis permits precise tuning of their properties. Here, by augmenting the internal positive charge within the α-hemolysin pore and varying its distribution, we increase the frequency of translocation of a 92-nt single-stranded DNA through the pore at +120 mV by ≈10-fold over the wild-type protein and dramatically lower the voltage threshold at which translocation occurs, e.g., by 50 mV for 1 event·s−1·μM−1. Further, events in which DNA enters the pore, but is not immediately translocated, are almost eliminated. These experiments provide a basis for improved nucleic acid analysis with protein nanopores, which might be translated to solid-state nanopores by using chemical surface modification. PMID:19060213

Picosecond laser ablation of poly-L-lactide: Effect of crystallinity on the material response

NASA Astrophysics Data System (ADS)

Ortiz, Rocío; Quintana, Iban; Etxarri, Jon; Lejardi, Ainhoa; Sarasua, Jose-Ramon

2011-11-01

The picosecond laser ablation of poly-L-lactide (PLLA) as a function of laser fluence and degree of crystallinity was examined. The ablation parameters and the surface modifications were analyzed under various irradiation conditions using laser wavelengths ranging from the ultraviolet through the visible. When processing the amorphous PLLA, both energy threshold and topography varied considerably depending on laser wavelength. Laser irradiation showed a reduction in the energy ablation threshold as the degree of crystallinity increased, probably related to photomechanical effects involved in laser ablation with ultra-short pulses and the lower stress accommodation behavior of semicrystalline polymers. In particular, cooperative chain motions are impeded by the higher degree of crystallinity, showing fragile mechanical behavior and lower energy dissipation. The experimental results on ablation rate versus laser energy showed that UV laser ablation on semicrystalline PLLA was more efficient than the visible ablation, i.e., it exhibits higher etch rates over a wide range of pulse energy conditions. These results were interpreted in terms of photo-thermal and photo-chemical response of polymers as a function of material micro-structure and incident laser wavelength. High quality micro-grooves were produced in amorphous PLLA, reveling the potential of ultra-fast laser processing technique in the field of micro-structuring biocompatible and biodegradable polymers for biomedical applications.

Use of Threshold of Toxicological Concern (TTC) with High Throughput Exposure Predictions as a Risk-Based Screening Approach to Prioritize More Than Seven Thousand Chemicals (ASCCT)

EPA Science Inventory

Here, we present results of an approach for risk-based prioritization using the Threshold of Toxicological Concern (TTC) combined with high-throughput exposure (HTE) modelling. We started with 7968 chemicals with calculated population median oral daily intakes characterized by an...

Dose Response Data for Hormonally Active Chemicals ...

EPA Pesticide Factsheets

The shape of the dose response curve in the low dose region has been debated since the late 1940s. The debate originally focused on linear no threshold (LNT) vs threshold responses in the low dose range for cancer and noncancer related effects. For noncancer effects the default assumption is that noncancer effects generally display threshold rather than LNT responses. More recently, claims have arisen that the chemicals, like endocrine disrupters (EDS), which act via high affinity, low capacity nuclear receptors, may display LNT or nonmonotonic low dose responses: responses that could be missed in multigenerational guideline toxicity testing. This presentation will discuss LNT, threshold and nonmonotonic dose response relationships from case studies of chemicals that disrupt reproductive development and function via the ER, AR and AhR pathways and will include in vitro and in vivo multigenerational data. The in vivo studies in this discussion include only robust, well designed, comprehensive studies that administered the chemical via a relevant route(s) of exposure over a broad dose response range, including low dose(s) in the microgram/kg/d range. The chemicals include ethinyl estradiol, estradiol, genistein, bisphenol a, trenbolone, finasteride, flutamide, phthalate esters and 2,3,7,8 TCDD. The objective is to critically evaluate the data from well done studies in this field to address concerns that current multigenerational reproductive test gui

Chemical modification of citrus pectin: Structural, physical and rheologial implications.

PubMed

Fracasso, Aline Francielle; Perussello, Camila Augusto; Carpiné, Danielle; Petkowicz, Carmen Lúcia de Oliveira; Haminiuk, Charles Windson Isidoro

2018-04-01

The present study aimed to investigate the physical, structural and rheological modifications caused by the chemical modification process of citrus pectin. Therefore, three commercial citrus pectins with different degree of esterification were chemically modified by sequential alkali and acidic hydrolytic process to produce modified citrus pectins (MCP) with special properties. The molar mass (M w ), degree of esterification (DE), monosaccharide composition, 13 C NMR spectra, homogeneity, morphology (SEM) and rheological behavior of both native and modified citrus pectins (MCP) were investigated. The chemical modification reduced the acid uronic content (up to 28.3%) and molar mass (up to 29.98%), however, showed little influence on the degree of esterification of native pectins. Modified citrus pectins presented higher amounts of neutral monosaccharides, mainly galactose, arabinose and rhamnose, typical of the Ramnogalacturonana-I (RG-I) region. Rheological tests indicated that the native and modified citrus pectins presented pseudoplastic behavior, however, the MCP samples were less viscous, compared to the native ones. Modified samples presented better dissolution in water and less strong gels, with good stability during oscillatory shearing at 25°C. This study aims to better understand the implications that chemical modifications may impose on the structure of citrus pectins. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical modification of semiconductor surfaces

NASA Technical Reports Server (NTRS)

Finklea, H. O.

1981-01-01

Results of research on the chemical modification of TiO2 powders in the gas phase and the examination of the modified powders by infrared absorption spectroscopy are comprehensively summarized. The range of information obtainable by IR spectroscopy of chemically modified semiconductors, and a definition of the optimum reaction conditions for synthesizing a monolayer of methylsilanes using vapor phase reaction conditions were considered.

Crab shell chitin whiskers reinforced natural rubber nanocomposites. 3. Effect of chemical modification of chitin whiskers.

PubMed

Gopalan Nair, Kalaprasad; Dufresne, Alain; Gandini, Alessandro; Belgacem, Mohamed Naceur

2003-01-01

The purpose of this study was to chemically modify the surface of chitin whiskers and to investigate the effect of the incorporation of these modified whiskers into a natural rubber (NR) matrix on the properties of the ensuing nanocomposite. Different chemical coupling agents were tested, namely, phenyl isocyanate (PI), alkenyl succinic anhydride (ASA) (Accosize 18 from American Cyanamid), and 3-isopropenyl-alpha,alpha'-dimethylbenzyl isocyanate (TMI). The extent of chemical modification was evaluated by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), and surface energy analysis. After chemical modification, nanocomposite films were obtained using a toluene natural rubber solution in which the whiskers were dispersed. Their mechanical properties were found to be inferior to those of unmodified chitin/NR composites presented in our previous study. In fact, even though there is an increase in filler-matrix interaction as a result of chemical modification of the chitin whiskers, this does not contribute to the improvement in the mechanical properties of the resulting nanocomposite. It is concluded that this loss of performance is due to the partial destruction of the three-dimensional network of chitin whiskers assumed to be present in the unmodified composites.

Redirecting adenovirus tropism by genetic, chemical, and mechanical modification of the adenovirus surface for cancer gene therapy.

PubMed

Yoon, A-Rum; Hong, Jinwoo; Kim, Sung Wan; Yun, Chae-Ok

2016-06-01

Despite remarkable advancements, clinical evaluations of adenovirus (Ad)-mediated cancer gene therapies have highlighted the need for improved delivery and targeting. Genetic modification of Ad capsid proteins has been extensively attempted. Although genetic modification enhances the therapeutic potential of Ad, it is difficult to successfully incorporate extraneous moieties into the capsid and the engineering process is laborious. Recently, chemical modification of the Ad surface with nanomaterials and targeting moieties has been found to enhance Ad internalization into the target by both passive and active mechanisms. Alternatively, external stimulus-mediated targeting can result in selective accumulation of Ad in the tumor and prevent dissemination of Ad into surrounding nontarget tissues. In the present review, we discuss various genetic, chemical, and mechanical engineering strategies for overcoming the challenges that hinder the therapeutic efficacy of Ad-based approaches. Surface modification of Ad by genetic, chemical, or mechanical engineering strategies enables Ad to overcome the shortcomings of conventional Ad and enhances delivery efficiency through distinct and unique mechanisms that unmodified Ad cannot mimic. However, although the therapeutic potential of Ad-mediated gene therapy has been enhanced by various surface modification strategies, each strategy still possesses innate limitations that must be addressed, requiring innovative ideas and designs.

Compositional threshold for Nuclear Waste Glass Durability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kruger, Albert A.; Farooqi, Rahmatullah; Hrma, Pavel R.

2013-04-24

Within the composition space of glasses, a distinct threshold appears to exist that separates "good" glasses, i.e., those which are sufficiently durable, from "bad" glasses of a low durability. The objective of our research is to clarify the origin of this threshold by exploring the relationship between glass composition, glass structure and chemical durability around the threshold region.

40 CFR Appendix B to Part 355 - The List of Extremely Hazardous Substances and Their Threshold Planning Quantities

Code of Federal Regulations, 2013 CFR

2013-07-01

... Substances and Their Threshold Planning Quantities B Appendix B to Part 355 Protection of Environment... Substances and Their Threshold Planning Quantities [CAS Number Order] CAS No. Chemical name Notes Reportable quantity *(pounds) Threshold planning quantity(pounds) 0 Organorhodium Complex (PMN-82-147) 10 10/10,000 50...

The influence of thresholds on the risk assessment of carcinogens in food.

PubMed

Pratt, Iona; Barlow, Susan; Kleiner, Juliane; Larsen, John Christian

2009-08-01

The risks from exposure to chemical contaminants in food must be scientifically assessed, in order to safeguard the health of consumers. Risk assessment of chemical contaminants that are both genotoxic and carcinogenic presents particular difficulties, since the effects of such substances are normally regarded as being without a threshold. No safe level can therefore be defined, and this has implications for both risk management and risk communication. Risk management of these substances in food has traditionally involved application of the ALARA (As Low as Reasonably Achievable) principle, however ALARA does not enable risk managers to assess the urgency and extent of the risk reduction measures needed. A more refined approach is needed, and several such approaches have been developed. Low-dose linear extrapolation from animal carcinogenicity studies or epidemiological studies to estimate risks for humans at low exposure levels has been applied by a number of regulatory bodies, while more recently the Margin of Exposure (MOE) approach has been applied by both the European Food Safety Authority and the Joint FAO/WHO Expert Committee on Food Additives. A further approach is the Threshold of Toxicological Concern (TTC), which establishes exposure thresholds for chemicals present in food, dependent on structure. Recent experimental evidence that genotoxic responses may be thresholded has significant implications for the risk assessment of chemicals that are both genotoxic and carcinogenic. In relation to existing approaches such as linear extrapolation, MOE and TTC, the existence of a threshold reduces the uncertainties inherent in such methodology and improves confidence in the risk assessment. However, for the foreseeable future, regulatory decisions based on the concept of thresholds for genotoxic carcinogens are likely to be taken case-by-case, based on convincing data on the Mode of Action indicating that the rate limiting variable for the development of cancer lies on a critical pathway that is thresholded.

Differences in taste detection thresholds between normal-weight and obese young adults.

PubMed

Park, Dong Choon; Yeo, Joon Hyung; Ryu, In Yong; Kim, Sang Hoon; Jung, Junyang; Yeo, Seung Geun

2015-05-01

Compared with normal-weight individuals, obese young adults exhibited a significantly higher taste threshold for salty taste. Smoking also affected taste functions in this population. The aim of this study was to investigate the differences in taste detection thresholds between normal-weight and obese young adults. Taste threshold was measured using electrogustometry (EGM) and chemically with sucrose, NaCl, citric acid, and quinine hydrochloride in 41 volunteers in their twenties, 23 with body mass index (BMI) <23 kg/m(2) (normal-weight group) and 18 with BMI >25 kg/m(2) (obese group). BMI was significantly higher in the obese than in the normal-weight group (p < 0.05). The obese group exhibited significantly higher EGM thresholds than the normal-weight group on the right (p < 0.05) and left (p < 0.05) posterior tongue. In chemical taste tests, the obese group had higher thresholds for sweet, salty, sour, and bitter tastes than the normal-weight group, although the difference in threshold was significant only for salty taste (p < 0.05). Smoking had an impact on taste threshold, with smokers having higher thresholds than non-smokers, with significantly higher EGM thresholds on the right anterior and posterior and the left anterior tongue (p < 0.05 each).

Key advances in the chemical modification of nanocelluloses.

PubMed

Habibi, Youssef

2014-03-07

Nanocelluloses, including nanocrystalline cellulose, nanofibrillated cellulose and bacterial cellulose nanofibers, have become fascinating building blocks for the design of new biomaterials. Derived from the must abundant and renewable biopolymer, they are drawing a tremendous level of attention, which certainly will continue to grow in the future driven by the sustainability trend. This growing interest is related to their unsurpassed quintessential physical and chemical properties. Yet, owing to their hydrophilic nature, their utilization is restricted to applications involving hydrophilic or polar media, which limits their exploitation. With the presence of a large number of chemical functionalities within their structure, these building blocks provide a unique platform for significant surface modification through various chemistries. These chemical modifications are prerequisite, sometimes unavoidable, to adapt the interfacial properties of nanocellulose substrates or adjust their hydrophilic-hydrophobic balance. Therefore, various chemistries have been developed aiming to surface-modify these nano-sized substrates in order to confer to them specific properties, extending therefore their use to highly sophisticated applications. This review collocates current knowledge in the research and development of nanocelluloses and emphasizes more particularly on the chemical modification routes developed so far for their functionalization.

An adaptive, comprehensive monitoring strategy for chemicals of emerging concern (CECs) in California's Aquatic Ecosystems.

PubMed

Maruya, Keith A; Schlenk, Daniel; Anderson, Paul D; Denslow, Nancy D; Drewes, Jörg E; Olivieri, Adam W; Scott, Geoffrey I; Snyder, Shane A

2014-01-01

A scientific advisory panel was convened by the State of California to recommend monitoring for chemicals of emerging concern (CECs) in aquatic systems that receive discharge of municipal wastewater treatment plant (WWTP) effluent and stormwater runoff. The panel developed a risk-based screening framework that considered environmental sources and fate of CECs observed in receiving waters across the State. Using existing occurrence and risk threshold data in water, sediment, and biological tissue, the panel applied the framework to identify a priority list of CECs for initial monitoring in three representative receiving water scenarios. The initial screening list of 16 CECs identified by the panel included consumer and commercial chemicals, flame retardants, pesticides, pharmaceuticals and personal care products, and natural hormones. The panel designed an iterative, phased strategy with interpretive guidelines that direct and update management actions commensurate with potential risk identified using the risk-based framework and monitoring data. Because of the ever-changing nature of chemical use, technology, and management practices, the panel offered recommendations to improve CEC monitoring, including development of bioanalytical screening methods whose responses integrate exposure to complex mixtures and that can be linked to higher-order effects; development or refinement of models that predict the input, fate, and effects of future chemicals; and filling of key data gaps on CEC occurrence and toxicity. Finally, the panel stressed the need for adaptive management, allowing for future review of, and if warranted, modifications to the strategy to incorporate the latest science available to the water resources community. © 2013 SETAC.

Thresholds of Toxicological Concern - Setting a threshold for testing below which there is little concern.

PubMed

Hartung, Thomas

2017-01-01

Low dose, low risk; very low dose, no real risk. Setting a pragmatic threshold below which concerns become negligible is the purpose of thresholds of toxicological concern (TTC). The idea is that such threshold values do not need to be established for each and every chemical based on experimental data, but that by analyzing the distribution of lowest or no-effect doses of many chemicals, a TTC can be defined - typically using the 5th percentile of this distribution and lowering it by an uncertainty factor of, e.g., 100. In doing so, TTC aims to compare exposure information (dose) with a threshold below which any hazard manifestation is very unlikely to occur. The history and current developments of this concept are reviewed and the application of TTC for different regulated products and their hazards is discussed. TTC lends itself as a pragmatic filter to deprioritize testing needs whenever real-life exposures are much lower than levels where hazard manifestation would be expected, a situation that is called "negligible exposure" in the REACH legislation, though the TTC concept has not been fully incorporated in its implementation (yet). Other areas and regulations - especially in the food sector and for pharmaceutical impurities - are more proactive. Large, curated databases on toxic effects of chemicals provide us with the opportunity to set TTC for many hazards and substance classes and thus offer a precautionary second tier for risk assessments if hazard cannot be excluded. This allows focusing testing efforts better on relevant exposures to chemicals.

76 FR 41365 - Impact of Reducing the Mixture Concentration Threshold for Commercial Schedule 2A Chemical...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-13

...The Bureau of Industry and Security (BIS) is seeking public comments on the impact of amending the Chemical Weapons Convention Regulations (CWCR) to reduce the concentration level below which the CWCR exempt certain mixtures containing a Schedule 2A chemical from the declaration requirements that apply to Schedule 2A chemical production, processing, and consumption under the Chemical Weapons Convention (CWC). To make these declaration requirements consistent with the international agreement adopted by the Organization for the Prohibition of Chemical Weapons (OPCW), BIS is considering amending the CWCR to replace the current low concentration exemption (a concentration of ``less than 30%'' by volume or weight) with a two-tiered low concentration exemption that is based, in part, on whether the total amount of a Schedule 2A chemical produced, processed, or consumed at one or more plants on a plant site during a calendar year is less than the applicable verification threshold in the CWCR. Under this two- tiered approach, the declaration and reporting requirements in the CWCR would not apply to a chemical mixture containing a Schedule 2A chemical if: The concentration of the Schedule 2A chemical in the mixture is ``1% or less,'' or the concentration of the Schedule 2A chemical in the mixture is ``more than 1%, but less than or equal to 10%,'' and the annual amount of the Schedule 2A chemical produced, processed, or consumed is less than the relevant verification threshold. Legislative amendment of the Chemical Weapons Convention Implementation Act (CWCIA) is required in order to implement this proposed amendment to the CWCR. In addition, at U.S. national discretion, BIS is considering amending the CWCR to require declarations/reports for exports and imports of any mixtures that contain ``more than 10%'' of a Schedule 2A chemical by volume or weight (whichever method yields the lesser percentage), if the total quantity of the Schedule 2A chemical exported or imported during a calendar year exceeds the applicable CWCR declaration threshold.

Improvements to the strength and corrosion resistance of aluminum-magnesium-manganese alloys of near-AA5083 chemistry

NASA Astrophysics Data System (ADS)

Carroll, Mark Christopher

Aluminum alloys of the 5000 series (AI-Mg-Mn) are extremely popular in a wide range of applications that call for a balance of moderately high strength, good corrosion resistance, and light weight, all at a moderate cost. One of the most popular 5000 series alloys is designated A1-5083, containing, in addition to aluminum, approximately 4 wt% magnesium and 0.7 wt% manganese. In order to increase the range of versatility of this particular alloy, a number of modifications have been examined that will potentially improve the strength and corrosion resistance characteristics while maintaining a chemical composition that is very close to the proven 5083 alloy. The strength of the 5083-based alloys under study are investigated with two goals in mind---to maximize the potential strength characteristics in a "standard" 5083 form through changes in minor processing parameters or through minor alloying additions. Increasing the standard alloy's potential is possible through improved efficiency of "preprocessing" heat treatments that maximize the homogeneous dispersion of secondary manganese-based particles. For the modified alloy study, additions of scandium and zirconium are shown to improve strength not only by forming secondary particles in the alloy, but also through substitutional solid solution strengthening, even when added at very small levels. Corrosion resistance of these 5083-based alloys is investigated once again through minor alloying additions; specifically zinc, copper, and silver. Zinc is particularly effective in that it changes the corrosion-susceptible binary aluminum-magnesium phase that would otherwise form on grain boundaries following exposure to moderately elevated temperatures for extended periods of time to a ternary aluminum-magnesium-zinc phase. This chemical composition of this ternary phase that forms following zinc additions can be further altered through minor additions of copper and silver. By determining threshold levels for these modifications while maintaining a chemical composition that is very near that of standard Al-5083, it can be shown that even minor modifications to processing and alloying parameters can have a favorable effect on the final bulk properties of the alloy. The increased range of strength and corrosion resistance of these lightly modified alloys make them more attractive in a broadened range of potential applications.

Heat-induced Irreversible Denaturation of the Camelid Single Domain VHH Antibody Is Governed by Chemical Modifications

PubMed Central

Akazawa-Ogawa, Yoko; Takashima, Mizuki; Lee, Young-Ho; Ikegami, Takahisa; Goto, Yuji; Uegaki, Koichi; Hagihara, Yoshihisa

2014-01-01

The variable domain of camelid heavy chain antibody (VHH) is highly heat-resistant and is therefore ideal for many applications. Although understanding the process of heat-induced irreversible denaturation is essential to improve the efficacy of VHH, its inactivation mechanism remains unclear. Here, we showed that chemical modifications predominantly governed the irreversible denaturation of VHH at high temperatures. After heat treatment, the activity of VHH was dependent only on the incubation time at 90 °C and was insensitive to the number of heating (90 °C)-cooling (20 °C) cycles, indicating a negligible role for folding/unfolding intermediates on permanent denaturation. The residual activity was independent of concentration; therefore, VHH lost its activity in a unimolecular manner, not by aggregation. A VHH mutant lacking Asn, which is susceptible to chemical modifications, had significantly higher heat resistance than did the wild-type protein, indicating the importance of chemical modifications to VHH denaturation. PMID:24739391

Enhancing the functional properties of thermophilic enzymes by chemical modification and immobilization.

PubMed

Cowan, Don A; Fernandez-Lafuente, Roberto

2011-09-10

The immobilization of proteins (mostly typically enzymes) onto solid supports is mature technology and has been used successfully to enhance biocatalytic processes in a wide range of industrial applications. However, continued developments in immobilization technology have led to more sophisticated and specialized applications of the process. A combination of targeted chemistries, for both the support and the protein, sometimes in combination with additional chemical and/or genetic engineering, has led to the development of methods for the modification of protein functional properties, for enhancing protein stability and for the recovery of specific proteins from complex mixtures. In particular, the development of effective methods for immobilizing large multi-subunit proteins with multiple covalent linkages (multi-point immobilization) has been effective in stabilizing proteins where subunit dissociation is the initial step in enzyme inactivation. In some instances, multiple benefits are achievable in a single process. Here we comprehensively review the literature pertaining to immobilization and chemical modification of different enzyme classes from thermophiles, with emphasis on the chemistries involved and their implications for modification of the enzyme functional properties. We also highlight the potential for synergies in the combined use of immobilization and other chemical modifications. Copyright © 2011 Elsevier Inc. All rights reserved.

Lanthanum doped strontium titanate - ceria anodes: deconvolution of impedance spectra and relationship with composition and microstructure

NASA Astrophysics Data System (ADS)

Burnat, Dariusz; Nasdaurk, Gunnar; Holzer, Lorenz; Kopecki, Michal; Heel, Andre

2018-05-01

Electrochemical performance of ceramic (Ni-free) SOFC anodes based on La0.2Sr0.7TiO3-δ (LST) and Gd0.1Ce0.9O1.95-δ (CGO) is thoroughly investigated. Microstructures and compositions are systematically varied around the percolation thresholds of both phases by modification of phase volume fractions, particle size distributions and firing temperature. Differential impedance spectroscopy was performed while varying gas composition, electrical potential and operating temperature, which allows determining four distinct electrode processes. Significant anode impedances are measured at low frequencies, which in contrast to the literature cannot be linked with gas concentration impedance. The dominant low frequency process (∼1 Hz) is attributed to the chemical capacitance. Combined EIS and microstructure investigations show that the chemical capacitance correlates inversely with the available surface area of CGO, indicating CGO surface reactions as the kinetic limitation for the dominant anode process and for the associated chemical capacitance. In anodes with a fine-grained microstructure this limitation is significantly smaller, which results in an impressive power output as high as 0.34 Wcm-2. The anodes show high redox stability by not only withstanding 30 isothermal redox cycles, but even improving the performance. Hence, compared to conventional Ni-cermet anodes the new LST-CGO material represents an interesting alternative with much improved redox-stability.

Modification of wheat starch with succinic acid/acetanhydride and azelaic acid/acetanhydride mixtures. II. Chemical and physical properties.

PubMed

Ačkar, Durđica; Subarić, Drago; Babić, Jurislav; Miličević, Borislav; Jozinović, Antun

2014-08-01

The aim of this research was to investigate the influence of modification with succinic acid/acetanhydride and azelaic acid/acetanhydride mixtures on chemical and physical properties of wheat starch. Starch was isolated from two wheat varieties and modified with mixtures of succinic acid and acetanhydride and azelaic acid and acetanhydride in 4, 6 and 8% (w/w). Total starch content, resistant starch content, degree of modification, changes in FT-IR spectra, colour, gel texture and freeze-thaw stability were determined. Results showed that resistant starch content increased by both investigated modifications, and degree of modification increased proportionally to amount of reagents used. FT-IR analysis of modified starches showed peak around 1,740 cm(-1), characteristic for carbonyl group of ester. Total colour difference caused by modifications was detectable by trained people. Adhesiveness significantly increased, while freeze-thaw stability decreased by both investigated modifications.

Effects of silicone hydrogel contact lens wear on ocular surface sensitivity to tactile, pneumatic mechanical, and chemical stimulation.

PubMed

Situ, Ping; Simpson, Trefford L; Jones, Lyndon W; Fonn, Desmond

2010-12-01

To determine the effects of silicone hydrogel lens wear and lens-solution interactions on ocular surface sensitivity. Forty-eight adapted lens wearers completed the study, which comprised two phases. Phase 1 included habitual lens wear, no lens wear (7 ± 3 days), and balafilcon A lenses (PV; PureVision; Bausch & Lomb, Rochester, NY) with a hydrogen peroxide-based regimen for 2 weeks; phase 2 included wear of PV with the use of a multipurpose solution containing either polyhexamethylene-biguanide (PHMB) or Polyquad/Aldox (Alcon Laboratories, Fort Worth, TX) preservative, each for 1 week, with a 2-week washout period between solutions. Tactile and pneumatic (mechanical and chemical) stimuli were delivered, and thresholds were determined by Cochet-Bonnet (Luneau Ophthalmologie, Chartres, France) and Belmonte (Cooperative Research Centre for Eye Research and Technology, Sydney, NSW, Australia) pneumatic esthesiometers, respectively. Corneal and conjunctival thresholds and staining scores were assessed at baseline, after 2 and 8 hours of lens wear on day 1 and at the end of each wearing cycle (2 hours). In phase 1, compared to the no-lens baseline, corneal tactile thresholds increased at the 1-day, 8-hour and the 2-week visits (P < 0.05), whereas conjunctival mechanical thresholds decreased at the 1-day, 2-hour and the 2-week visits (P < 0.05). In phase 2, the chemical thresholds were lower with PHMB-preserved solution compared with the Polyquad/Aldox system at the 1-day, 2-hour and the 1-week visits (P < 0.05). Staining scores correlated inversely with conjunctival chemical thresholds (all P < 0.05). Ocular surface sensitivity changed in adapted lens wearers, when lenses were refit after a no-lens interval and during lens wear with different care regimens. The corneal staining that was observed with certain lens-solution combinations was accompanied by sensory alteration of the ocular surface-that is, higher levels of staining correlated with increased conjunctival chemical sensitivity. (ClinicalTrials.gov number, NCT00455455.).

Two-color above-threshold and two-photon sequential double ionization beyond the dipole approximation

NASA Astrophysics Data System (ADS)

Grum-Grzhimailo, A. N.; Gryzlova, E. V.; Kuzmina, E. I.; Chetverkina, A. S.; Strakhova, S. I.

2015-04-01

Two nonlinear atomic photoprocesses are theoretically considered with the emphasis on the photoelectron angular distributions and their modifications due to violation of the dipole approximation: sequential two-photon double ionization and two-color above threshold ionization. These reactions are now accessible with X-ray free electron lasers. Both processes are exemplified by the ionization of krypton: from the 4p shell in the sequential two-photon double ionization and from the 2s shell in the two-color above-threshold ionization, which are compared to the Ar(3p) and Ne(1s) ionization, respectively. Noticeable nondipole effects are predicted.

Evaluating Energy Conversion Efficiency

NASA Technical Reports Server (NTRS)

Byvik, C. E.; Smith, B. T.; Buoncristiani, A. M.

1983-01-01

Devices that convert solar radiation directly into storable chemical or electrical energy, have characteristic energy absorption spectrum; specifically, each of these devices has energy threshold. The conversion efficiency of generalized system that emcompasses all threshold devices is analyzed, resulting in family of curves for devices of various threshold energies operating at different temperatures.

D-optimal experimental designs to test for departure from additivity in a fixed-ratio mixture ray.

PubMed

Coffey, Todd; Gennings, Chris; Simmons, Jane Ellen; Herr, David W

2005-12-01

Traditional factorial designs for evaluating interactions among chemicals in a mixture may be prohibitive when the number of chemicals is large. Using a mixture of chemicals with a fixed ratio (mixture ray) results in an economical design that allows estimation of additivity or nonadditive interaction for a mixture of interest. This methodology is extended easily to a mixture with a large number of chemicals. Optimal experimental conditions can be chosen that result in increased power to detect departures from additivity. Although these designs are used widely for linear models, optimal designs for nonlinear threshold models are less well known. In the present work, the use of D-optimal designs is demonstrated for nonlinear threshold models applied to a fixed-ratio mixture ray. For a fixed sample size, this design criterion selects the experimental doses and number of subjects per dose level that result in minimum variance of the model parameters and thus increased power to detect departures from additivity. An optimal design is illustrated for a 2:1 ratio (chlorpyrifos:carbaryl) mixture experiment. For this example, and in general, the optimal designs for the nonlinear threshold model depend on prior specification of the slope and dose threshold parameters. Use of a D-optimal criterion produces experimental designs with increased power, whereas standard nonoptimal designs with equally spaced dose groups may result in low power if the active range or threshold is missed.

Chemical Modification of Cyclodextrin and Amylose by Click Reaction and Its Application to the Synthesis of Poly-alkylamine-Modified Antibacterial Sugars.

PubMed

Yamamura, Hatsuo

2017-01-01

Cyclodextrin (CD) can be chemically modified into desired and sophisticated functional molecules. However, poly-modification often produces complicated mixtures, resulting in a low yield of the desired product. As the most promising procedure to solve such problems and to achieve poly-modification of the CD molecule, we present here the Huisgen 1,3-dipolar cycloaddition, known as a click reaction. This review will describe the results of our microwave-assisted click reaction for the poly-modification of CD and amylose molecules, and its application to the study of synthetic membrane active antibacterial derivatives.

Analysis of Publically Available Skin Sensitization Data from REACH Registrations 2008–2014

PubMed Central

Luechtefeld, Thomas; Maertens, Alexandra; Russo, Daniel P.; Rovida, Costanza; Zhu, Hao; Hartung, Thomas

2017-01-01

Summary The public data on skin sensitization from REACH registrations already included 19,111 studies on skin sensitization in December 2014, making it the largest repository of such data so far (1,470 substances with mouse LLNA, 2,787 with GPMT, 762 with both in vivo and in vitro and 139 with only in vitro data). 21% were classified as sensitizers. The extracted skin sensitization data was analyzed to identify relationships in skin sensitization guidelines, visualize structural relationships of sensitizers, and build models to predict sensitization. A chemical with molecular weight > 500 Da is generally considered non-sensitizing owing to low bioavailability, but 49 sensitizing chemicals with a molecular weight > 500 Da were found. A chemical similarity map was produced using PubChem’s 2D Tanimoto similarity metric and Gephi force layout visualization. Nine clusters of chemicals were identified by Blondel’s module recognition algorithm revealing wide module-dependent variation. Approximately 31% of mapped chemicals are Michael’s acceptors but alone this does not imply skin sensitization. A simple sensitization model using molecular weight and five ToxTree structural alerts showed a balanced accuracy of 65.8% (specificity 80.4%, sensitivity 51.4%), demonstrating that structural alerts have information value. A simple variant of k-nearest neighbors outperformed the ToxTree approach even at 75% similarity threshold (82% balanced accuracy at 0.95 threshold). At higher thresholds, the balanced accuracy increased. Lower similarity thresholds decrease sensitivity faster than specificity. This analysis scopes the landscape of chemical skin sensitization, demonstrating the value of large public datasets for health hazard prediction. PMID:26863411

Thio-amide functionalized polymers via polymerization or post-polymerization modification

NASA Astrophysics Data System (ADS)

Ozcam, Ali; Henke, Adam; Stibingerova, Iva; Srogl, Jiri; Genzer, Jan

2011-03-01

Decreasing supplies of fresh water and increasing population necessitates development of advanced water cleaning technologies, which would facilitate the removal of water pollutants. Amongst the worst of such contaminants are heavy metals and cyanides, infamous for their high toxicity. To assist the water purification processes, we aim to synthesize functionalized macromolecules that would contribute in the decontamination processes by scavenging detrimental chemicals. Epitomizing this role thio-amide unit features remarkable chemical flexibility that facilitates reversible catch-release of the ions, where the behavior controlled by subtle red-ox changes in the environment. Chemical tunability of the thio-amide moiety enables synthesis of thio-amide based monomers and post-polymerization modification agents. Two distinct synthetic pathways, polymerization and post-polymerization modification, have been exploited, leading to functional thioamide-based macromolecules: thioamide-monomers were copolymerized with N-isopropylacrylamide and post-polymerization modifications of poly(dimethylaminoethyl methacrylate) and poly(propargyl methacrylate) were accomplished via quarternization and ``click'' reactions, respectively.

Enzyme Technology of Peroxidases: Immobilization, Chemical and Genetic Modification

NASA Astrophysics Data System (ADS)

Longoria, Adriana; Tinoco, Raunel; Torres, Eduardo

An overview of enzyme technology applied to peroxidases is made. Immobilization on organic, inorganic, and hybrid supports; chemical modification of amino acids and heme group; and genetic modification by site-directed and random mutagenesis are included. Different strategies that were carried out to improve peroxidase performance in terms of stability, selectivity, and catalytic activity are analyzed. Immobilization of peroxidases on inorganic and organic materials enhances the tolerance of peroxidases toward the conditions normally found in many industrial processes, such as the presence of an organic solvent and high temperature. In addition, it is shown that immobilization helps to increase the Total Turnover Number at levels high enough to justify the use of a peroxidase-based biocatalyst in a synthesis process. Chemical modification of peroxidases produces modified enzymes with higher thermostability and wider substrate variability. Finally, through mutagenesis approaches, it is possible to produce modified peroxidases capable of oxidizing nonnatural substrates with high catalytic activity and affinity.

Marine exposure of preservative-treated small wood panels

Treesearch

B. R. Johnson; D. I. Gutzmer

1984-01-01

Small wood panels treated with many different chemicals have been exposed to limnorian and teredine marine borers in the sea at Key West, Florida. These preservatives and treatments include creosotes with and without modification, waterborne salts, salt-creosote dual treatments, chemical modifications of wood, and modified polymers. In spite of the accelerated nature...

Chemical and Biological Tools for the Preparation of Modified Histone Proteins

PubMed Central

Howard, Cecil J.; Yu, Ruixuan R.; Gardner, Miranda L.; Shimko, John C.; Ottesen, Jennifer J.

2016-01-01

Eukaryotic chromatin is a complex and dynamic system in which the DNA double helix is organized and protected by interactions with histone proteins. This system is regulated through, a large network of dynamic post-translational modifications (PTMs) exists to ensure proper gene transcription, DNA repair, and other processes involving DNA. Homogenous protein samples with precisely characterized modification sites are necessary to better understand the functions of modified histone proteins. Here, we discuss sets of chemical and biological tools that have been developed for the preparation of modified histones, with a focus on the appropriate choice of tool for a given target. We start with genetic approaches for the creation of modified histones, including the incorporation of genetic mimics of histone modifications, chemical installation of modification analogs, and the use of the expanded genetic code to incorporate modified amino acids. Additionally, we will cover the chemical ligation techniques that have been invaluable in the generation of complex modified histones that are indistinguishable from the natural counterparts. Finally, we will end with a prospectus on future directions of synthetic chromatin in living systems. PMID:25863817

Preliminay Investigation of Variation in Some Dark Adaptation Aspects fo Possible Relevance to Military Helicopter Aircrew.

DTIC Science & Technology

1983-06-01

Niven, J.I., McFarland, R.A., and Roughton, F.J. Variations in Visual Thresholds During Carbon Monoxide and Hypoxic Anoxia (abstract). Fed. Proc...and Niven, J.I. Visual Thresholds as an Index of the Modification of the Effects of Anoxia by Glucose. Am. J. Physiol. 144:378-88. 1945. 71... Diphosphoglycerate and Night Vision. Aviat. Space Environ. Med. 52(1):41-44. 1981. 100. Sexton, M., Malone, F. and Farnsworth, D. The Effect of Ultra- violet

Sulfenic acid chemistry, detection and cellular lifetime☆

PubMed Central

Gupta, Vinayak; Carroll, Kate S.

2014-01-01

Background Reactive oxygen species-mediated cysteine sulfenic acid modification has emerged as an important regulatory mechanism in cell signaling. The stability of sulfenic acid in proteins is dictated by the local microenvironment and ability of antioxidants to reduce this modification. Several techniques for detecting this cysteine modification have been developed, including direct and in situ methods. Scope of review This review presents a historical discussion of sulfenic acid chemistry and highlights key examples of this modification in proteins. A comprehensive survey of available detection techniques with advantages and limitations is discussed. Finally, issues pertaining to rates of sulfenic acid formation, reduction, and chemical trapping methods are also covered. Major conclusions Early chemical models of sulfenic acid yielded important insights into the unique reactivity of this species. Subsequent pioneering studies led to the characterization of sulfenic acid formation in proteins. In parallel, the discovery of oxidant-mediated cell signaling pathways and pathological oxidative stress has led to significant interest in methods to detect these modifications. Advanced methods allow for direct chemical trapping of protein sulfenic acids directly in cells and tissues. At the same time, many sulfenic acids are short-lived and the reactivity of current probes must be improved to sample these species, while at the same time, preserving their chemical selectivity. Inhibitors with binding scaffolds can be rationally designed to target sulfenic acid modifications in specific proteins. General significance Ever increasing roles for protein sulfenic acids have been uncovered in physiology and pathology. A more complete understanding of sulfenic acid-mediated regulatory mechanisms will continue to require rigorous and new chemical insights. This article is part of a Special Issue entitled Current methods to study reactive oxygen species - pros and cons and biophysics of membrane proteins. Guest Editor: Christine Winterbourn. PMID:23748139

Effect of Reduction of Redox Modifications of Cys-Residues in the Na,K-ATPase α1-Subunit on Its Activity

PubMed Central

Dergousova, Elena A.; Petrushanko, Irina Yu.; Klimanova, Elizaveta A.; Mitkevich, Vladimir A.; Ziganshin, Rustam H.; Lopina, Olga D.; Makarov, Alexander A.

2017-01-01

Sodium-potassium adenosine triphosphatase (Na,K-ATPase) creates a gradient of sodium and potassium ions necessary for the viability of animal cells, and it is extremely sensitive to intracellular redox status. Earlier we found that regulatory glutathionylation determines Na,K-ATPase redox sensitivity but the role of basal glutathionylation and other redox modifications of cysteine residues is not clear. The purpose of this study was to detect oxidized, nitrosylated, or glutathionylated cysteine residues in Na,K-ATPase, evaluate the possibility of removing these modifications and assess their influence on the enzyme activity. To this aim, we have detected such modifications in the Na,K-ATPase α1-subunit purified from duck salt glands and tried to eliminate them by chemical reducing agents and the glutaredoxin1/glutathione reductase enzyme system. Detection of cysteine modifications was performed using mass spectrometry and Western blot analysis. We have found that purified Na,K-ATPase α1-subunit contains glutathionylated, nitrosylated, and oxidized cysteines. Chemical reducing agents partially eliminate these modifications that leads to the slight increase of the enzyme activity. Enzyme system glutaredoxin/glutathione reductase, unlike chemical reducing agents, produces significant increase of the enzyme activity. At the same time, the enzyme system deglutathionylates native Na,K-ATPase to a lesser degree than chemical reducing agents. This suggests that the enzymatic reducing system glutaredoxin/glutathione reductase specifically affects glutathionylation of the regulatory cysteine residues of Na,K-ATPase α1-subunit. PMID:28230807

Aryl-modified graphene quantum dots with enhanced photoluminescence and improved pH tolerance

NASA Astrophysics Data System (ADS)

Luo, Peihui; Ji, Zhe; Li, Chun; Shi, Gaoquan

2013-07-01

Chemical modification is an important technique to modulate the chemical and optical properties of graphene quantum dots (GQDs). In this paper, we report a versatile diazonium chemistry method to graft aryl groups including phenyl, 4-carboxyphenyl, 4-sulfophenyl and 5-sulfonaphthyl to GQDs via Gomberg-Bachmann reaction. The aryl-modified GQDs are nanocrystals with lateral dimensions in the range of 2-4 nm and an average thickness lower than 1 nm. Upon chemical modification with aryl groups, the photoluminescence (PL) bands of GQDs were tuned in the range of 418 and 447 nm, and their fluorescence quantum yields (QYs) were increased for up to about 6 times. Furthermore, the aryl-modified GQDs exhibited stable PL (both intensity and peak position) in a wide pH window of 1-11. The mechanism of improving the PL properties of GQDs by aryl-modification was also discussed.Chemical modification is an important technique to modulate the chemical and optical properties of graphene quantum dots (GQDs). In this paper, we report a versatile diazonium chemistry method to graft aryl groups including phenyl, 4-carboxyphenyl, 4-sulfophenyl and 5-sulfonaphthyl to GQDs via Gomberg-Bachmann reaction. The aryl-modified GQDs are nanocrystals with lateral dimensions in the range of 2-4 nm and an average thickness lower than 1 nm. Upon chemical modification with aryl groups, the photoluminescence (PL) bands of GQDs were tuned in the range of 418 and 447 nm, and their fluorescence quantum yields (QYs) were increased for up to about 6 times. Furthermore, the aryl-modified GQDs exhibited stable PL (both intensity and peak position) in a wide pH window of 1-11. The mechanism of improving the PL properties of GQDs by aryl-modification was also discussed. Electronic supplementary information (ESI) available: Fluorescence quantum yield measurements, estimation of grafting ratio, TEM images, FTIR spectra, PL spectra and zeta potentials. See DOI: 10.1039/c3nr02156d

The Unexpected and Exceptionally Facile Chemical Modification of the Phenolic Hydroxyl Group of Tyrosine by Polyhalogenated Quinones under Physiological Conditions.

PubMed

Qu, Na; Li, Feng; Shao, Bo; Shao, Jie; Zhai, Guijin; Wang, Fuyi; Zhu, Ben-Zhan

2016-10-17

The phenolic hydroxyl group of tyrosine residue plays a crucial role in the structure and function of many proteins. However, little study has been reported about its modification by chemical agents under physiological conditions. In this study, we found, unexpectedly, that the phenolic hydroxyl group of tyrosine can be rapidly and efficiently modified by tetrafluoro-1,4-benzoquinone and other polyhalogenated quinones, which are the major genotoxic and carcinogenic quinoid metabolites of polyhalogenated aromatic compounds. The modification was found to be mainly due to the formation of a variety of fluoroquinone-O-tyrosine conjugates and their hydroxylated derivatives via nucleophilic substitution pathway. Analogous modifications were observed for tyrosine-containing peptides. Further studies showed that the blockade of the reactive phenolic hydroxyl group of tyrosine in the substrate peptide, even by very low concentration of tetrafluoro-1,4-benzoquinone, can prevent the kinase catalyzed tyrosine phosphorylation. This is the first report showing the exceptionally facile chemical modification of the phenolic hydroxyl group of tyrosine by polyhalogenated quinones under normal physiological conditions, which may have potential biological and toxicological implications.

Identification and classification of carcinogens: procedures of the Chemical Substances Threshold Limit Value Committee, ACGIH. American Conference of Governmental Industrial Hygienists.

PubMed Central

Spirtas, R; Steinberg, M; Wands, R C; Weisburger, E K

1986-01-01

The Chemical Substances Threshold Limit Value Committee of the American Conference of Governmental Industrial Hygienists has refined its procedures for evaluating carcinogens. Types of epidemiologic and toxicologic evidence used are reviewed and a discussion is presented on how the Committee evaluates data on carcinogenicity. Although it has not been conclusively determined whether biological thresholds exist for all types of carcinogens, the Committee will continue to develop guidelines for permissible exposures to carcinogens. The Committee will continue to use the safety factor approach to setting Threshold Limit Values for carcinogens, despite its shortcomings. A compilation has been developed for lists of substances considered to be carcinogenic by several scientific groups. The Committee will use this information to help to identify and classify carcinogens for its evaluation. PMID:3752326

Identification and classification of carcinogens: procedures of the Chemical Substances Threshold Limit Value Committee, ACGIH. American Conference of Governmental Industrial Hygienists

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spirtas, R.; Steinberg, M.; Wands, R.C.

1986-10-01

The Chemical Substances Threshold Limit Value Committee of the American Conference of Governmental Industrial Hygienists has refined its procedures for evaluating carcinogens. Types of epidemiologic and toxicologic evidence used are reviewed and a discussion is presented on how the Committee evaluates data on carcinogenicity. Although it has not been conclusively determined whether biological thresholds exist for all types of carcinogens, the Committee will continue to develop guidelines for permissible exposures to carcinogens. The Committee will continue to use the safety factor approach to setting Threshold Limit Values for carcinogens, despite its shortcomings. A compilation has been developed for lists ofmore » substances considered to be carcinogenic by several scientific groups. The Committee will use this information to help to identify and classify carcinogens for its evaluation.« less

Dynamic and Tunable Threshold Voltage in Organic Electrochemical Transistors.

PubMed

Doris, Sean E; Pierre, Adrien; Street, Robert A

2018-04-01

In recent years, organic electrochemical transistors (OECTs) have found applications in chemical and biological sensing and interfacing, neuromorphic computing, digital logic, and printed electronics. However, the incorporation of OECTs in practical electronic circuits is limited by the relative lack of control over their threshold voltage, which is important for controlling the power consumption and noise margin in complementary and unipolar circuits. Here, the threshold voltage of OECTs is precisely tuned over a range of more than 1 V by chemically controlling the electrochemical potential at the gate electrode. This threshold voltage tunability is exploited to prepare inverters and amplifiers with improved noise margin and gain, respectively. By coupling the gate electrode with an electrochemical oscillator, single-transistor oscillators based on OECTs with dynamic time-varying threshold voltages are prepared. This work highlights the importance of electrochemistry at the gate electrode in determining the electrical properties of OECTs, and opens a path toward the system-level design of low-power OECT-based electronics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

No-threshold dose-response curves for nongenotoxic chemicals: Findings and applications for risk assessment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheehan, Daniel M.

2006-01-15

We tested the hypothesis that no threshold exists when estradiol acts through the same mechanism as an active endogenous estrogen. A Michaelis-Menten (MM) equation accounting for response saturation, background effects, and endogenous estrogen level fit a turtle sex-reversal data set with no threshold and estimated the endogenous dose. Additionally, 31 diverse literature dose-response data sets were analyzed by adding a term for nonhormonal background; good fits were obtained but endogenous dose estimations were not significant due to low resolving power. No thresholds were observed. Data sets were plotted using a normalized MM equation; all 178 data points were accommodated onmore » a single graph. Response rates from {approx}1% to >95% were well fit. The findings contradict the threshold assumption and low-dose safety. Calculating risk and assuming additivity of effects from multiple chemicals acting through the same mechanism rather than assuming a safe dose for nonthresholded curves is appropriate.« less

2009 Toxic Chemical Release Inventory Report for the Emergency Planning and Community Right-to-Know Act of 1986, Title III, Section 313

DOE Office of Scientific and Technical Information (OSTI.GOV)

Environmental Stewardship Group

For reporting year 2009, Los Alamos National Laboratory (LANL) submitted a Form R report for lead as required under the Emergency Planning and Community Right-to- Know Act (EPCRA) Section 313. No other EPCRA Section 313 chemicals were used in 2009 above the reportable thresholds. This document was prepared to provide a description of the evaluation of EPCRA Section 313 chemical use and threshold determinations for LANL for calendar year 2009, as well as to provide background information about data included on the Form R reports.

Impact of the excess sludge modification with selected chemical reagents on the increase of dissolved organic substances concentration compounds transformations in activated sludge.

PubMed

Zawieja, Iwona; Lidia, Wolny; Marta, Próba

2017-07-01

Submission of excess sludge initial disintegration process significantly affects the efficiency of anaerobic stabilization process. Expression of increasing the concentration of organic matter in dissolved form is to increase sludge disintegration. As a result of chemical modification is an increase of the chemical oxygen demand and the concentration of volatile fatty acids. The aim of this study was to determine the impact of the disintegration process with selected chemical reagents to increase the concentration of organic substances in dissolved form. The process of chemical disintegration of excess sludge was treated using the following reagents: Mg(OH) 2 , Ca(OH) 2 , HCl, H 2 SO 4 , H 2 O 2 . The modification was carried out at ambient temperature for 2, 6 and 24h. During sludge disintegration it was noticed the growth of indicators values that confirmed the susceptibility of prepared sludge to biodegradation. Copyright © 2017 Elsevier Inc. All rights reserved.

Mechanisms of carcinogensis: dose response

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gehring, P.J.; Blau, G.E.

There is great controversy whether the carcinogenicity of chemicals is dose-dependent and whether a threshold dose exists below which cancer will not be induced by exposure. Evidence for dose-dependency exists and is believed to be accepted generally if extricated as it should be from the threshold concept. The threshold concept conflict is not likely to be resolved in the foreseeable future; proponents and opponents argue their case in a manner similar to those arguing religion. In this paper the various arguments are reviewed. Subsequently, a chemical process model for carcinogenesis is developed based on the generally accepted evidence that themore » carcinogenic activity of many chemicals can be related to electrophilic alkylation of DNA. Using this model, some incidence of cancer, albeit negligible, will be predicted regardless how low the dose. However, the model revelas that the incidence of cancer induced by real-life exposures is likely to be greatly overestimated by currently used stochastic statistical extrapolations. Even more important, modeling of the chemical processes involved in the fate of a carcinogenic chemical in the body reveals experimental approaches to elucidating the mechanism(s) of carcinogenesis and ultimately a more scientifically sound basis for assessing the hazard of low-level exposure to a chemical carcinogen.« less

Effects of channel modifications on the hydrology of Chicod Creek basin, North Carolina, 1975-87

USGS Publications Warehouse

Mason, R.R.; Simmons, C.E.; Watkins, S.A.

1990-01-01

Drainage modifications in this Coastal Plain basin from 1978 to 1981 consisted of channel excavation and clearing of blockages. A study was begun in 1975 to define hydrologic conditions of the basin before, during, and after modifications and to determine what changes were attributed to modifications. Surface-water conditions were altered during and following modifications. Minimum flow at Juniper Branch was increased from less than 0.1 cu ft/sec to 0.4 cu ft/second;streamflow variability was reduced from an index of 0.87 to 0.49. In-channel velocity at Chicod Creek was increased from a mean of 0.4 ft/sec to 1.5 ft/sec. Substantial groundwater level declines were observed in wells 180 and 250 ft from Juniper Branch during the modifications phase;these were 0.4 and 0.2 ft, respectively. However, most surface-water and groundwater conditions returned nearly to premodification levels by 1987. Water-quality characteristics monitored during the investigation included physical, chemical, and bacteriological characteristics. Physical characteristics monitored were suspended sediment, temperature, dissolved oxygen, and pH. Of these physical characteristics, only sediment concentrations increased substantially during channel modifications. Chemical characteristics studied were major dissolved constituents, nutrients, trace metals, and pesticides. Substantial changes ranged from a decline in total iron concentrations of 77% to an increase in total nitrite concentrations of 130%. Changes in many chemical characteristics persisted following channel modifications. Bacterial counts did not change substantially.

QCM operating in threshold mode as a gas sensor.

PubMed

Dultsev, Fedor N; Kolosovsky, Eugeny A

2009-10-20

Application of the threshold mode allowed us to use the quartz resonator (quartz crystal microbalance, QCM) as a highly sensitive gas sensor measuring the forces of the rupture of adsorbed gas components from the resonator surface oscillating with increasing amplitude. This procedure allows one to analyze different gas components using the same surface modification, just varying the rupture threshold by varying the amplitude of shear oscillations. The sensitivity of the threshold measurements is 2 to 3 orders of magnitude higher than for the gravimetric procedure. It is demonstrated that the QCM operating as an active element can be used as a gas sensor. This procedure seems to be promising in investigating the reactivity of the surface or the interactions of gaseous components with the surface containing various functional groups, thus contributing to the surface chemistry.

An integrated evaluation of some faecal indicator bacteria (FIB) and chemical markers as potential tools for monitoring sewage contamination in subtropical estuaries.

PubMed

Cabral, Ana Caroline; Stark, Jonathan S; Kolm, Hedda E; Martins, César C

2018-04-01

Sewage input and the relationship between chemical markers (linear alkylbenzenes and coprostanol) and fecal indicator bacteria (FIB, Escherichia coli and enterococci), were evaluated in order to establish thresholds values for chemical markers in suspended particulate matter (SPM) as indicators of sewage contamination in two subtropical estuaries in South Atlantic Brazil. Both chemical markers presented no linear relationship with FIB due to high spatial microbiological variability, however, microbiological water quality was related to coprostanol values when analyzed by logistic regression, indicating that linear models may not be the best representation of the relationship between both classes of indicators. Logistic regression was performed with all data and separately for two sampling seasons, using 800 and 100 MPN 100 mL -1 of E. coli and enterococci, respectively, as the microbiological limits of sewage contamination. Threshold values of coprostanol varied depending on the FIB and season, ranging between 1.00 and 2.23 μg g -1 SPM. The range of threshold values of coprostanol for SPM are relatively higher and more variable than those suggested in literature for sediments (0.10-0.50 μg g -1 ), probably due to higher concentration of coprostanol in SPM than in sediment. Temperature may affect the relationship between microbiological indicators and coprostanol, since the threshold value of coprostanol found here was similar to tropical areas, but lower than those found during winter in temperate areas, reinforcing the idea that threshold values should be calibrated for different climatic conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Identification of novel uncertainty factors and thresholds of toxicological concern for health hazard and risk assessment: Application to cleaning product ingredients.

PubMed

Wang, Zhen; Scott, W Casan; Williams, E Spencer; Ciarlo, Michael; DeLeo, Paul C; Brooks, Bryan W

2018-04-01

Uncertainty factors (UFs) are commonly used during hazard and risk assessments to address uncertainties, including extrapolations among mammals and experimental durations. In risk assessment, default values are routinely used for interspecies extrapolation and interindividual variability. Whether default UFs are sufficient for various chemical uses or specific chemical classes remains understudied, particularly for ingredients in cleaning products. Therefore, we examined publicly available acute median lethal dose (LD50), and reproductive and developmental no-observed-adverse-effect level (NOAEL) and lowest-observed-adverse-effect level (LOAEL) values for the rat model (oral). We employed probabilistic chemical toxicity distributions to identify likelihoods of encountering acute, subacute, subchronic and chronic toxicity thresholds for specific chemical categories and ingredients in cleaning products. We subsequently identified thresholds of toxicological concern (TTC) and then various UFs for: 1) acute (LD50s)-to-chronic (reproductive/developmental NOAELs) ratios (ACRs), 2) exposure duration extrapolations (e.g., subchronic-to-chronic; reproductive/developmental), and 3) LOAEL-to-NOAEL ratios considering subacute/acute developmental responses. These ratios (95% CIs) were calculated from pairwise threshold levels using Monte Carlo simulations to identify UFs for all ingredients in cleaning products. Based on data availability, chemical category-specific UFs were also identified for aliphatic acids and salts, aliphatic alcohols, inorganic acids and salts, and alkyl sulfates. In a number of cases, derived UFs were smaller than default values (e.g., 10) employed by regulatory agencies; however, larger UFs were occasionally identified. Such UFs could be used by assessors instead of relying on default values. These approaches for identifying mammalian TTCs and diverse UFs represent robust alternatives to application of default values for ingredients in cleaning products and other chemical classes. Findings can also support chemical substitutions during alternatives assessment, and data dossier development (e.g., read across), identification of TTCs, and screening-level hazard and risk assessment when toxicity data is unavailable for specific chemicals. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of chemically modified wood on bond durability

Treesearch

Rishawn Brandon; Rebecca E. Ibach; Charles R. Frihart

2005-01-01

Chemical modification of wood can improve its dimensional stability and resistance to biological degradation and moisture, but modification can also create a new surface for bonding. Acetylation of wood results in the loss of hydroxyl groups, making the wood more hydrophobic and reduces its ability to hydrogen-bond with the adhesive. In contrast, reacting wood with...

Ultrasonic modification of carbon materials for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Rachiy, Bogdan I.; Nykoliuk, Marian O.; Budzulyak, Ivan M.; Kachmar, Andrii I.

2017-01-01

The paper is devoted to study the ultrasonic impact on the biomass of natural raw materials, which were used for the creation a nanoporous carbon material (NCM), which was used as electrode material for electrochemical capacitors (EC). The dry shells of apricot seeds were a feedstock, which were modified by the chemical treatment in the phosphoric acid and part of them were impacted by ultrasonic waves for 25 minutes. The NCM, which were obtained by carbonization at 550 °C, were modified by chemical treatment in the nitric acid. Thus, the different of modification NCM was obtained to compare their capacitance characteristics for EC. From experimental data we can do a conclusion, that ultrasonic modification and chemical treatment in nitric acidare improvecapacitance characteristics of NCM for EC.

Recent advances in the chemical modification of unsaturated polymers

NASA Technical Reports Server (NTRS)

Schulz, D. N.; Turner, S. R.; Golub, M. A.

1982-01-01

The present discussion has the objective to update the most comprehensive reviews on the considered subject and to fill in the gaps of less complete, but more modern treatments. Only simple chemical functionalization or structural modification of unsaturated polymers are covered, and the literature of diene polymer modification since 1974 is emphasized. Attention is given to hydrogenation, halogenation and hydrohalogenation, cyclization, cis-trans isomerization, epoxidation, ene and other cycloaddition reactions, sulfonation, carboxylation, phosphonylation, sulfenyl chloride addition, carbene addition, metalation, and silylation. It is pointed out that modern synthetic reagents and catalysts have been advantageously employed to improve process and/or product quality. Synthetic techniques have been refined to allow the selective modification of specific polymer microstructures or blocks.

Ionospheric chemical releases

NASA Technical Reports Server (NTRS)

Bernhardt, Paul A.; Scales, W. A.

1990-01-01

Ionospheric plasma density irregularities can be produced by chemical releases into the upper atmosphere. F-region plasma modification occurs by: (1) chemically enhancing the electron number density; (2) chemically reducing the electron population; or (3) physically convecting the plasma from one region to another. The three processes (production, loss, and transport) determine the effectiveness of ionospheric chemical releases in subtle and surprising ways. Initially, a chemical release produces a localized change in plasma density. Subsequent processes, however, can lead to enhanced transport in chemically modified regions. Ionospheric modifications by chemical releases excites artificial enhancements in airglow intensities by exothermic chemical reactions between the newly created plasma species. Numerical models were developed to describe the creation and evolution of large scale density irregularities and airglow clouds generated by artificial means. Experimental data compares favorably with theses models. It was found that chemical releases produce transient, large amplitude perturbations in electron density which can evolve into fine scale irregularities via nonlinear transport properties.

Diazo Compounds: Versatile Tools for Chemical Biology.

PubMed

Mix, Kalie A; Aronoff, Matthew R; Raines, Ronald T

2016-12-16

Diazo groups have broad and tunable reactivity. That and other attributes endow diazo compounds with the potential to be valuable reagents for chemical biologists. The presence of diazo groups in natural products underscores their metabolic stability and anticipates their utility in a biological context. The chemoselectivity of diazo groups, even in the presence of azido groups, presents many opportunities. Already, diazo compounds have served as chemical probes and elicited novel modifications of proteins and nucleic acids. Here, we review advances that have facilitated the chemical synthesis of diazo compounds, and we highlight applications of diazo compounds in the detection and modification of biomolecules.

Harnessing epigenome modifications for better crops

USDA-ARS?s Scientific Manuscript database

Chemical DNA modifications such as methylation influence translation of the DNA code to specific genetic outcomes. While such modifications can be heritable, others are transient, and their overall contribution to plant genetic diversity remains intriguing but uncertain. The focus of this article is...

Communication: Polarizable polymer chain under external electric field in a dilute polymer solution.

PubMed

Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

2015-11-28

We study the conformational behavior of polarizable polymer chain under an external homogeneous electric field within the Flory type self-consistent field theory. We consider the influence of electric field on the polymer coil as well as on the polymer globule. We show that when the polymer chain conformation is a coil, application of external electric field leads to its additional swelling. However, when the polymer conformation is a globule, a sufficiently strong field can induce a globule-coil transition. We show that such "field-induced" globule-coil transition at the sufficiently small monomer polarizabilities goes quite smoothly. On the contrary, when the monomer polarizability exceeds a certain threshold value, the globule-coil transition occurs as a dramatic expansion in the regime of first-order phase transition. The developed theoretical model can be applied to predicting polymer globule density change under external electric field in order to provide more efficient processes of polymer functionalization, such as sorption, dyeing, and chemical modification.

Getting the Message? Native Reactive Electrophiles Pass Two Out of Three Thresholds to be Bona Fide Signaling Mediators.

PubMed

Poganik, Jesse R; Long, Marcus J C; Aye, Yimon

2018-05-01

Precision cell signaling activities of reactive electrophilic species (RES) are arguably among the most poorly-understood means to transmit biological messages. Latest research implicates native RES to be a chemically-distinct subset of endogenous redox signals that influence cell decision making through non-enzyme-assisted modifications of specific proteins. Yet, fundamental questions remain regarding the role of RES as bona fide second messengers. Here, we lay out three sets of criteria we feel need to be met for RES to be considered as true cellular signals that directly mediate information transfer by modifying "first-responding" sensor proteins. We critically assess the available evidence and define the extent to which each criterion has been fulfilled. Finally, we offer some ideas on the future trajectories of the electrophile signaling field taking inspiration from work that has been done to understand canonical signaling mediators. Also see the video abstract here: https://youtu.be/rG7o0clVP0c. © 2018 WILEY Periodicals, Inc.

Chemical sensing thresholds for mine detection dogs

NASA Astrophysics Data System (ADS)

Phelan, James M.; Barnett, James L.

2002-08-01

Mine detection dogs have been found to be an effective method to locate buried landmines. The capabilities of the canine olfaction method are from a complex combination of training and inherent capacity of the dog for odor detection. The purpose of this effort was to explore the detection thresholds of a limited group of dogs that were trained specifically for landmine detection. Soils were contaminated with TNT and 2,4-DNT to develop chemical vapor standards to present to the dogs. Soils contained ultra trace levels of TNT and DNT, which produce extremely low vapor levels. Three groups of dogs were presented the headspace vapors from the contaminated soils in work environments for each dog group. One positive sample was placed among several that contained clean soils and, the location and vapor source (strength, type) was frequently changed. The detection thresholds for the dogs were determined from measured and extrapolated dilution of soil chemical residues and, estimated soil vapor values using phase partitioning relationships. The results showed significant variances in dog sensing thresholds, where some dogs could sense the lowest levels and others had trouble with even the highest source. The remarkable ultra-trace levels detectable by the dogs are consistent with the ultra-trace chemical residues derived from buried landmines; however, poor performance may go unnoticed without periodic challenge tests at levels consistent with performance requirements.

Structure-based design of novel chemical modification of the 3'-overhang for optimization of short interfering RNA performance.

PubMed

Xu, Lexing; Wang, Xin; He, Hongwei; Zhou, Jinming; Li, Xiaoyu; Ma, Hongtao; Li, Zelin; Zeng, Yi; Shao, Rongguang; Cen, Shan; Wang, Yucheng

2015-02-10

Short interfering RNAs (siRNAs) are broadly used to manipulate gene expression in mammalian cells. Although chemical modification is useful for increasing the potency of siRNAs in vivo, rational optimization of siRNA performance through chemical modification is still a challenge. In this work, we designed and synthesized a set of siRNAs containing modified two-nucleotide 3'-overhangs with the aim of strengthening the interaction between the 3'-end of the siRNA strand and the PAZ domain of Ago2. Their efficiency of binding to the PAZ domain was calculated using a computer modeling program, followed by measurement of RNA-Ago2 interaction in a surface plasmon resonance biochemical assay. The results suggest that increasing the level of binding of the 3'-end of the guiding strand with the PAZ domain, and/or reducing the level of binding of the sense strand through modifying the two-nucleotide 3'-overhangs, affects preferential strand selection and improves siRNA activity, while we cannot exclude the possibility that the modifications at the 3'-end of the sense strand may also affect the recognition of the 5'-end of the guiding strand by the MID domain. Taken together, our work presents a strategy for optimizing siRNA performance through asymmetric chemical modification of 3'-overhangs and also helps to develop the computer modeling method for rational siRNA design.

Surface modification of protein enhances encapsulation in chitosan nanoparticles

NASA Astrophysics Data System (ADS)

Koyani, Rina D.; Andrade, Mariana; Quester, Katrin; Gaytán, Paul; Huerta-Saquero, Alejandro; Vazquez-Duhalt, Rafael

2018-04-01

Chitosan nanoparticles have a huge potential as nanocarriers for environmental and biomedical purposes. Protein encapsulation in nano-sized chitosan provides protection against inactivation, proteolysis, and other alterations due to environmental conditions, as well as the possibility to be targeted to specific tissues by ligand functionalization. In this work, we demonstrate that the chemical modification of the protein surface enhances the protein loading in chitosan nanocarriers. Encapsulation of green fluorescent protein and the cytochrome P450 was studied. The increase of electrostatic interactions between the free amino groups of chitosan and the increased number of free carboxylic groups in the protein surface enhance the protein loading, protein retention, and, thus, the enzymatic activity of chitosan nanoparticles. The chemical modification of protein surface with malonic acid moieties reduced drastically the protein isoelectric point increasing the protein interaction with the polycationic biomaterial and chitosan. The chemical modification of protein does not alter the morphology of chitosan nanoparticles that showed an average diameter of 18 nm, spheroidal in shape, and smooth surfaced. The strategy of chemical modification of protein surface, shown here, is a simple and efficient technique to enhance the protein loading in chitosan nanoparticles. This technique could be used for other nanoparticles based on polycationic or polyanionic materials. The increase of protein loading improves, doubtless, the performance of protein-loaded chitosan nanoparticles for biotechnological and biomedical applications.

Chemically Patterned Inverse Opal Created by a Selective Photolysis Modification Process.

PubMed

Tian, Tian; Gao, Ning; Gu, Chen; Li, Jian; Wang, Hui; Lan, Yue; Yin, Xianpeng; Li, Guangtao

2015-09-02

Anisotropic photonic crystal materials have long been pursued for their broad applications. A novel method for creating chemically patterned inverse opals is proposed here. The patterning technique is based on selective photolysis of a photolabile polymer together with postmodification on released amine groups. The patterning method allows regioselective modification within an inverse opal structure, taking advantage of selective chemical reaction. Moreover, combined with the unique signal self-reporting feature of the photonic crystal, the fabricated structure is capable of various applications, including gradient photonic bandgap and dynamic chemical patterns. The proposed method provides the ability to extend the structural and chemical complexity of the photonic crystal, as well as its potential applications.

Final Rule: Community Right-To-Know Reporting Requirements Federal Register Notice

EPA Pesticide Factsheets

Final reporting thresholds and threshold planning quantity (TPQ) for extremely hazardous substances (EHS) and non-EHS hazardous chemicals, required under Emergency Planning and Community Right-to-Know Act, Superfund Amendments and Reauthorization Act.

A screen of chemical modifications identifies position-specific modification by UNA to most potently reduce siRNA off-target effects

PubMed Central

Bramsen, Jesper B.; Pakula, Malgorzata M.; Hansen, Thomas B.; Bus, Claus; Langkjær, Niels; Odadzic, Dalibor; Smicius, Romualdas; Wengel, Suzy L.; Chattopadhyaya, Jyoti; Engels, Joachim W.; Herdewijn, Piet; Wengel, Jesper; Kjems, Jørgen

2010-01-01

Small interfering RNAs (siRNAs) are now established as the preferred tool to inhibit gene function in mammalian cells yet trigger unintended gene silencing due to their inherent miRNA-like behavior. Such off-target effects are primarily mediated by the sequence-specific interaction between the siRNA seed regions (position 2–8 of either siRNA strand counting from the 5′-end) and complementary sequences in the 3′UTR of (off-) targets. It was previously shown that chemical modification of siRNAs can reduce off-targeting but only very few modifications have been tested leaving more to be identified. Here we developed a luciferase reporter-based assay suitable to monitor siRNA off-targeting in a high throughput manner using stable cell lines. We investigated the impact of chemically modifying single nucleotide positions within the siRNA seed on siRNA function and off-targeting using 10 different types of chemical modifications, three different target sequences and three siRNA concentrations. We found several differently modified siRNAs to exercise reduced off-targeting yet incorporation of the strongly destabilizing unlocked nucleic acid (UNA) modification into position 7 of the siRNA most potently reduced off-targeting for all tested sequences. Notably, such position-specific destabilization of siRNA–target interactions did not significantly reduce siRNA potency and is therefore well suited for future siRNA designs especially for applications in vivo where siRNA concentrations, expectedly, will be low. PMID:20453030

Chemically Derivatized Semiconductor Photoelectrodes.

ERIC Educational Resources Information Center

Wrighton, Mark S.

1983-01-01

Deliberate modification of semiconductor photoelectrodes to improve durability and enhance rate of desirable interfacial redox processes is discussed for a variety of systems. Modification with molecular-based systems or with metals/metal oxides yields results indicating an important role for surface modification in devices for fundamental study…

EPCRA Instructions to the Tier II Emergency and Hazardous Chemical Inventory Form

EPA Pesticide Factsheets

The form is required for Tier Two reporting of hazardous chemicals in quantities equal to or greater than established threshold amounts. Sections include chemical description, hazard categories from both EPA and OSHA, and storage details.

Stormwater filtration of toxic heavy metal ions using lignocellulosic materials selection process, fiberization, chemical modification, and mat formation

Treesearch

James S. Han

1999-01-01

Lignocellulosic materials were evaluated for their effectiveness in filtering toxic heavy metals from stormwater. Kenaf, alfalfa, juniper, and aspen fibers were used as models to evaluate the effectiveness and limitations of chemical modification and the extent of fiber degradation. Individual and mixed aqueous solutions of nickel, copper, zinc, and cadmium in various...

Enhancing the functionality of cotton fabric by physical and chemical pre-treatments: A comparative study.

PubMed

Gargoubi, Sondes; Tolouei, Ranna; Chevallier, Pascale; Levesque, Lucie; Ladhari, Neji; Boudokhane, Chedly; Mantovani, Diego

2016-08-20

Recently, antimicrobial and decontaminating textiles, such as cotton a natural carbohydrate polymer, are generating more attention. Plant materials used for natural dyes are expected to impart biofunctional properties and high added valued functional textiles. In the current study, surface modification of cotton to maximize the dye amount on the surface has been investigated. Physical modification using nitrogen-hydrogen plasma, chemical modification using chitosan and chemical modification using dopamine as biopolymers imparting amino groups were explored. Furthermore, dye exhaustion of curcumin, as a natural functional dye has been studied. Dye stability tests were also performed after fabric washing using hospital washing protocol to predict the durability of the functionalizations. The results demonstrated that cotton surfaces treated with dopamine exhibit a high level of dye uptake (78%) and a good washing fastness. The use of non-toxic and natural additives during cotton finishing process could give the opportunity of cradle to cradle design for antimicrobial textile industries. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ultrasonic modification of carbon materials for electrochemical capacitors.

PubMed

Rachiy, Bogdan I; Nykoliuk, Marian O; Budzulyak, Ivan M; Kachmar, Andrii I

2017-12-01

The paper is devoted to study the ultrasonic impact on the biomass of natural raw materials, which were used for the creation a nanoporous carbon material (NCM), which was used as electrode material for electrochemical capacitors (EC). The dry shells of apricot seeds were a feedstock, which were modified by the chemical treatment in the phosphoric acid and part of them were impacted by ultrasonic waves for 25 minutes. The NCM, which were obtained by carbonization at 550 °C, were modified by chemical treatment in the nitric acid. Thus, the different of modification NCM was obtained to compare their capacitance characteristics for EC. From experimental data we can do a conclusion, that ultrasonic modification and chemical treatment in nitric acidare improvecapacitance characteristics of NCM for EC.

Selective Modification of Chitin and Chitosan: En Route to Tailored Oligosaccharides.

PubMed

Carvalho, Luísa C R; Queda, Fausto; Santos, Cátia V Almeida; Marques, M Manuel B

2016-12-19

Chitin and chitosan are attractive biopolymers with enormous structural possibilities for chemical modification, creating platforms for new chemical entities with a broad scope of applications, ranging from material science to medicine. During the last few years, incredible efforts have been dedicated to the regioselective modification of these biopolymers paving the way for improved properties and tailored activities. Herein, the most recent advances in chitin/chitosan regioselective modification, reaction conditions, selectivity, and the impact on its applications are highlighted. Moreover, the recent focus on chitooligosaccharides, their regioselective and chemoselective functionalization, as well as their role in biological studies, including molecular recognition with several biological targets are also covered. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Source term evaluation for combustion modeling

NASA Technical Reports Server (NTRS)

Sussman, Myles A.

1993-01-01

A modification is developed for application to the source terms used in combustion modeling. The modification accounts for the error of the finite difference scheme in regions where chain-branching chemical reactions produce exponential growth of species densities. The modification is first applied to a one-dimensional scalar model problem. It is then generalized to multiple chemical species, and used in quasi-one-dimensional computations of shock-induced combustion in a channel. Grid refinement studies demonstrate the improved accuracy of the method using this modification. The algorithm is applied in two spatial dimensions and used in simulations of steady and unsteady shock-induced combustion. Comparisons with ballistic range experiments give confidence in the numerical technique and the 9-species hydrogen-air chemistry model.

Improved Bat Algorithm Applied to Multilevel Image Thresholding

PubMed Central

2014-01-01

Multilevel image thresholding is a very important image processing technique that is used as a basis for image segmentation and further higher level processing. However, the required computational time for exhaustive search grows exponentially with the number of desired thresholds. Swarm intelligence metaheuristics are well known as successful and efficient optimization methods for intractable problems. In this paper, we adjusted one of the latest swarm intelligence algorithms, the bat algorithm, for the multilevel image thresholding problem. The results of testing on standard benchmark images show that the bat algorithm is comparable with other state-of-the-art algorithms. We improved standard bat algorithm, where our modifications add some elements from the differential evolution and from the artificial bee colony algorithm. Our new proposed improved bat algorithm proved to be better than five other state-of-the-art algorithms, improving quality of results in all cases and significantly improving convergence speed. PMID:25165733

Effect of threshold disorder on the quorum percolation model

NASA Astrophysics Data System (ADS)

Monceau, Pascal; Renault, Renaud; Métens, Stéphane; Bottani, Samuel

2016-07-01

We study the modifications induced in the behavior of the quorum percolation model on neural networks with Gaussian in-degree by taking into account an uncorrelated Gaussian thresholds variability. We derive a mean-field approach and show its relevance by carrying out explicit Monte Carlo simulations. It turns out that such a disorder shifts the position of the percolation transition, impacts the size of the giant cluster, and can even destroy the transition. Moreover, we highlight the occurrence of disorder independent fixed points above the quorum critical value. The mean-field approach enables us to interpret these effects in terms of activation probability. A finite-size analysis enables us to show that the order parameter is weakly self-averaging with an exponent independent on the thresholds disorder. Last, we show that the effects of the thresholds and connectivity disorders cannot be easily discriminated from the measured averaged physical quantities.

A Vastly Increased Chemical Variety of RNA Modifications Containing a Thioacetal Structure.

PubMed

Dal Magro, Christina; Keller, Patrick; Kotter, Annika; Werner, Stephan; Duarte, Victor; Marchand, Virginie; Ignarski, Michael; Freiwald, Anja; Müller, Roman-Ulrich; Dieterich, Christoph; Motorin, Yuri; Butter, Falk; Atta, Mohamed; Helm, Mark

2018-06-25

Recently discovered new chemical entities in RNA modifications have involved surprising functional groups that enlarge the chemical space of RNA. Using LC-MS, we found over 100 signals of RNA constituents that contained a ribose moiety in tRNAs from E. coli. Feeding experiments with variegated stable isotope labeled compounds identified 37 compounds that are new structures of RNA modifications. One structure was elucidated by deuterium exchange and high-resolution mass spectrometry. The structure of msms 2 i 6 A (2-methylthiomethylenethio-N6-isopentenyl-adenosine) was confirmed by methione-D3 feeding experiments and by synthesis of the nucleobase. The msms 2 i 6 A contains a thioacetal, shown in vitro to be biosynthetically derived from ms 2 i 6 A by the radical-SAM enzyme MiaB. This enzyme performs thiomethylation, forming ms 2 i 6 A from i 6 A in a first turnover. The new thioacetal is formed by a second turnover. Along with the pool of 36 new modifications, this work describes a new layer of RNA modification chemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coatings with controlled porosity and chemical properties

DOEpatents

Frye, Gregory C.; Brinker, C. Jeffrey; Doughty, Daniel H.; Bein, Thomas; Moller, Karin

1996-01-01

Coatings and sensors having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided.

Coatings with controlled porosity and chemical properties

DOEpatents

Frye, Gregory C.; Brinker, C. Jeffrey; Doughty, Daniel H.; Bein, Thomas; Moller, Karin

1993-01-01

Coatings and sensors having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided.

Single-event effects experienced by astronauts and microelectronic circuits flown in space

DOE Office of Scientific and Technical Information (OSTI.GOV)

McNulty, P.J.

Models developed for explaining the light flashes experienced by astronauts on Apollo and Skylab missions were used with slight modification to explain upsets observed in microelectronic circuits. Both phenomena can be explained by the simple assumption that an event occurs whenever a threshold number of ionizations or isomerizations are generated within a sensitive volume. Evidence is consistent with the threshold being sharp in both cases, but fluctuations in the physical stimuli lead to a gradual rather than sharp increase in cross section with LET. Successful use of the model requires knowledge of the dimensions of the sensitive volume and themore » value of threshold. Techniques have been developed to determine these SEU parameters in modern circuits.« less

Influence of major-groove chemical modifications of DNA on transcription by bacterial RNA polymerases

PubMed Central

Raindlová, Veronika; Janoušková, Martina; Slavíčková, Michaela; Perlíková, Pavla; Boháčová, Soňa; Milisavljevič, Nemanja; Šanderová, Hana; Benda, Martin; Barvík, Ivan; Krásný, Libor; Hocek, Michal

2016-01-01

DNA templates containing a set of base modifications in the major groove (5-substituted pyrimidines or 7-substituted 7-deazapurines bearing H, methyl, vinyl, ethynyl or phenyl groups) were prepared by PCR using the corresponding base-modified 2′-deoxyribonucleoside triphosphates (dNTPs). The modified templates were used in an in vitro transcription assay using RNA polymerase from Bacillus subtilis and Escherichia coli. Some modified nucleobases bearing smaller modifications (H, Me in 7-deazapurines) were perfectly tolerated by both enzymes, whereas bulky modifications (Ph at any nucleobase) and, surprisingly, uracil blocked transcription. Some middle-sized modifications (vinyl or ethynyl) were partly tolerated mostly by the E. coli enzyme. In all cases where the transcription proceeded, full length RNA product with correct sequence was obtained indicating that the modifications of the template are not mutagenic and the inhibition is probably at the stage of initiation. The results are promising for the development of bioorthogonal reactions for artificial chemical switching of the transcription. PMID:27001521

Artificial specific binders directly recovered from chemically modified nucleic acid libraries.

PubMed

Kasahara, Yuuya; Kuwahara, Masayasu

2012-01-01

Specific binders comprised of nucleic acids, that is, RNA/DNA aptamers, are attractive functional biopolymers owing to their potential broad application in medicine, food hygiene, environmental analysis, and biological research. Despite the large number of reports on selection of natural DNA/RNA aptamers, there are not many examples of direct screening of chemically modified nucleic acid aptamers. This is because of (i) the inferior efficiency and accuracy of polymerase reactions involving transcription/reverse-transcription of modified nucleotides compared with those of natural nucleotides, (ii) technical difficulties and additional time and effort required when using modified nucleic acid libraries, and (iii) ambiguous efficacies of chemical modifications in binding properties until recently; in contrast, the effects of chemical modifications on biostability are well studied using various nucleotide analogs. Although reports on the direct screening of a modified nucleic acid library remain in the minority, chemical modifications would be essential when further functional expansion of nucleic acid aptamers, in particular for medical and biological uses, is considered. This paper focuses on enzymatic production of chemically modified nucleic acids and their application to random screenings. In addition, recent advances and possible future research are also described.

Microwave plasma induced surface modification of diamond-like carbon films

NASA Astrophysics Data System (ADS)

Rao Polaki, Shyamala; Kumar, Niranjan; Gopala Krishna, Nanda; Madapu, Kishore; Kamruddin, Mohamed; Dash, Sitaram; Tyagi, Ashok Kumar

2017-12-01

Tailoring the surface of diamond-like carbon (DLC) film is technically relevant for altering the physical and chemical properties, desirable for useful applications. A physically smooth and sp3 dominated DLC film with tetrahedral coordination was prepared by plasma-enhanced chemical vapor deposition technique. The surface of the DLC film was exposed to hydrogen, oxygen and nitrogen plasma for physical and chemical modifications. The surface modification was based on the concept of adsorption-desorption of plasma species and surface entities of films. Energetic chemical species of microwave plasma are adsorbed, leading to desorbtion of the surface carbon atoms due to energy and momentum exchange. The interaction of such reactive species with DLC films enhanced the roughness, surface defects and dangling bonds of carbon atoms. Adsorbed hydrogen, oxygen and nitrogen formed a covalent network while saturating the dangling carbon bonds around the tetrahedral sp3 valency. The modified surface chemical affinity depends upon the charge carriers and electron covalency of the adsorbed atoms. The contact angle of chemically reconstructed surface increases when a water droplet interacts either through hydrogen or van dear Waals bonding. These weak interactions influenced the wetting property of the DLC surface to a great extent.

Chemical Modification of Waste Cotton Linters for Oil Spill Cleanup Application

NASA Astrophysics Data System (ADS)

Chattopadhyay, Debapriya; Umrigar, Keval

2017-12-01

The possibility of use of waste cotton linters as oil sorbents by chemical modification such as acetylation and cyanoethylation was studied. The acetylation process was carried out in presence of acetic anhydride using either H2SO4 or HClO4 as catalyst. The acetylation treatment time was 30, 60 and 120 min and treatment temperature was room temperature, 50 and 70 °C. For cyanoethylation, the waste cotton linters were pre-treated with 2, 5 and 10% NaOH. The treatment temperature for cyanoethylation was room temperature, 50 and 70 °C and treatment time was 30, 60 and 120 min. Both the chemical modification processes were optimized on the basis of oil absorption capacity of the chemically modified cotton fibre with the help of MATLAB software. The modified samples were tested for its oleophilicity in terms of oil absorption capacity, oil retention capacity, oil recovery capacity, reusability of sample and water uptake and buoyancy as oil sorbent. Chemically modified fibres were characterized by Fourier transform infra red spectrophotometer, scanning electron microscope and degree of substitutions.

Is ``No-Threshold'' a ``Non-Concept''?

NASA Astrophysics Data System (ADS)

Schaeffer, David J.

1981-11-01

A controversy prominent in scientific literature that has carried over to newspapers, magazines, and popular books is having serious social and political expressions today: “Is there, or is there not, a threshold below which exposure to a carcinogen will not induce cancer?” The distinction between establishing the existence of this threshold (which is a theoretical question) and its value (which is an experimental one) gets lost in the scientific arguments. Establishing the existence of this threshold has now become a philosophical question (and an emotional one). In this paper I qualitatively outline theoretical reasons why a threshold must exist, discuss experiments which measure thresholds on two chemicals, and describe and apply a statistical method for estimating the threshold value from exposure-response data.

Coatings with controlled porosity and chemical properties

DOEpatents

Frye, G.C.; Brinker, C.J.; Doughty, D.H.; Bein, T.; Moller, K.

1996-12-31

Coatings and sensors are disclosed having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided. 7 figs.

Coatings with controlled porosity and chemical properties

DOEpatents

Frye, G.C.; Brinker, C.J.; Doughty, D.H.; Bein, T.; Moller, K.

1993-07-06

Coatings and sensors are described having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided.

TTCs for oral exposure: Identification of outliers in Cramer class I, II and III using the combined database of RepDose (FhG), Toxbase (TNO), Munro and ToxRefDB (USEPA)

EPA Science Inventory

The Thresholds of Toxicological Concern (TTC) are generic human exposure threshold for structural groups of chemicals below which no risk to human health is assumed and therefore no further testing is needed. Different thresholds have been developed for oral exposure e.g. for gen...

Theoretical and experimental approaches to possible thresholds of response in carcinogenicity

EPA Science Inventory

The determination and utilization of the actual low dose-response relationship for chemical carcinogens has long interested toxicologists, experimental pathologists, modelers and risk assessors. To date, no unequivocal examples of carcinogenic thresholds in humans are known. Ho...

Discovery of a Chemical Modification by Citric Acid in a Recombinant Monoclonal Antibody

PubMed Central

2015-01-01

Recombinant therapeutic monoclonal antibodies exhibit a high degree of heterogeneity that can arise from various post-translational modifications. The formulation for a protein product is to maintain a specific pH and to minimize further modifications. Generally Recognized as Safe (GRAS), citric acid is commonly used for formulation to maintain a pH at a range between 3 and 6 and is generally considered chemically inert. However, as we reported herein, citric acid covalently modified a recombinant monoclonal antibody (IgG1) in a phosphate/citrate-buffered formulation at pH 5.2 and led to the formation of so-called “acidic species” that showed mass increases of 174 and 156 Da, respectively. Peptide mapping revealed that the modification occurred at the N-terminus of the light chain. Three additional antibodies also showed the same modification but displayed different susceptibilities of the N-termini of the light chain, heavy chain, or both. Thus, ostensibly unreactive excipients under certain conditions may increase heterogeneity and acidic species in formulated recombinant monoclonal antibodies. By analogy, other molecules (e.g., succinic acid) with two or more carboxylic acid groups and capable of forming an anhydride may exhibit similar reactivities. Altogether, our findings again reminded us that it is prudent to consider formulations as a potential source for chemical modifications and product heterogeneity. PMID:25136741

Improving CRISPR-Cas specificity with chemical modifications in single-guide RNAs.

PubMed

Ryan, Daniel E; Taussig, David; Steinfeld, Israel; Phadnis, Smruti M; Lunstad, Benjamin D; Singh, Madhurima; Vuong, Xuan; Okochi, Kenji D; McCaffrey, Ryan; Olesiak, Magdalena; Roy, Subhadeep; Yung, Chong Wing; Curry, Bo; Sampson, Jeffrey R; Bruhn, Laurakay; Dellinger, Douglas J

2018-01-25

CRISPR systems have emerged as transformative tools for altering genomes in living cells with unprecedented ease, inspiring keen interest in increasing their specificity for perfectly matched targets. We have developed a novel approach for improving specificity by incorporating chemical modifications in guide RNAs (gRNAs) at specific sites in their DNA recognition sequence ('guide sequence') and systematically evaluating their on-target and off-target activities in biochemical DNA cleavage assays and cell-based assays. Our results show that a chemical modification (2'-O-methyl-3'-phosphonoacetate, or 'MP') incorporated at select sites in the ribose-phosphate backbone of gRNAs can dramatically reduce off-target cleavage activities while maintaining high on-target performance, as demonstrated in clinically relevant genes. These findings reveal a unique method for enhancing specificity by chemically modifying the guide sequence in gRNAs. Our approach introduces a versatile tool for augmenting the performance of CRISPR systems for research, industrial and therapeutic applications. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Improving CRISPR–Cas specificity with chemical modifications in single-guide RNAs

PubMed Central

Ryan, Daniel E; Taussig, David; Steinfeld, Israel; Phadnis, Smruti M; Lunstad, Benjamin D; Singh, Madhurima; Vuong, Xuan; Okochi, Kenji D; McCaffrey, Ryan; Olesiak, Magdalena; Roy, Subhadeep; Yung, Chong Wing; Curry, Bo; Sampson, Jeffrey R; Dellinger, Douglas J

2018-01-01

Abstract CRISPR systems have emerged as transformative tools for altering genomes in living cells with unprecedented ease, inspiring keen interest in increasing their specificity for perfectly matched targets. We have developed a novel approach for improving specificity by incorporating chemical modifications in guide RNAs (gRNAs) at specific sites in their DNA recognition sequence (‘guide sequence’) and systematically evaluating their on-target and off-target activities in biochemical DNA cleavage assays and cell-based assays. Our results show that a chemical modification (2′-O-methyl-3′-phosphonoacetate, or ‘MP’) incorporated at select sites in the ribose-phosphate backbone of gRNAs can dramatically reduce off-target cleavage activities while maintaining high on-target performance, as demonstrated in clinically relevant genes. These findings reveal a unique method for enhancing specificity by chemically modifying the guide sequence in gRNAs. Our approach introduces a versatile tool for augmenting the performance of CRISPR systems for research, industrial and therapeutic applications. PMID:29216382

Chemical Structure and Surface Modification of Dendritic Nanomaterials Tailored for Therapeutic and Diagnostic Applications.

PubMed

Myung, Ja Hye; Hsu, Hao-Jui; Bugno, Jason; Tam, Kevin A; Hong, Seungpyo

2017-01-01

Dendritic nanomaterials have attracted a great deal of scientific interest due to their high capacity for multifunctionalization and potential in various biomedical applications, such as drug/gene delivery and diagnostic systems. Depending on the molecular structure and starting monomers, several different types of dendrimers have been developed, including poly(amidoamine) (PAMAM), poly(propylenimine) (PPI), and poly(L-lysine) (PLL) dendrimers, in addition to modified dendritic nanomaterials, such as Janus dendrimers and dendritic block copolymers. The chemical structure and surface modification of dendritic nanomaterials have been found to play a critical role in governing their biological behaviors. In this review, we present a comprehensive overview focusing on the synthesis and chemical structures of dendrimers and modified dendritic nanomaterials that are currently being investigated for drug delivery, gene delivery, and diagnostic applications. In addition, the impact of chemical surface modification and functionalization to the dendritic nanomaterials on their therapeutic and diagnostic applications are highlighted. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

15 CFR 713.2 - Annual declaration requirements for plant sites that produce, process or consume Schedule 2...

Code of Federal Regulations, 2012 CFR

2012-01-01

... a chemical in any units within the same plant through chemical reaction, including any associated... plant sites that produce, process or consume Schedule 2 chemicals in excess of specified thresholds. 713... (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS...

15 CFR 713.2 - Annual declaration requirements for plant sites that produce, process or consume Schedule 2...

Code of Federal Regulations, 2013 CFR

2013-01-01

... a chemical in any units within the same plant through chemical reaction, including any associated... plant sites that produce, process or consume Schedule 2 chemicals in excess of specified thresholds. 713... (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS...

15 CFR 713.2 - Annual declaration requirements for plant sites that produce, process or consume Schedule 2...

Code of Federal Regulations, 2014 CFR

2014-01-01

... a chemical in any units within the same plant through chemical reaction, including any associated... plant sites that produce, process or consume Schedule 2 chemicals in excess of specified thresholds. 713... (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS...

15 CFR 713.2 - Annual declaration requirements for plant sites that produce, process or consume Schedule 2...

Code of Federal Regulations, 2011 CFR

2011-01-01

... a chemical in any units within the same plant through chemical reaction, including any associated... plant sites that produce, process or consume Schedule 2 chemicals in excess of specified thresholds. 713... (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS...

Principles for identification of High Potency Category Chemicals for which the Dermal Sensitisation Threshold (DST) approach should not be applied.

PubMed

Roberts, David W; Api, Anne Marie; Safford, Robert J; Lalko, Jon F

2015-08-01

An essential step in ensuring the toxicological safety of chemicals used in consumer products is the evaluation of their skin sensitising potential. The sensitising potency, coupled with information on exposure levels, can be used in a Quantitative Risk Assessment (QRA) to determine an acceptable level of a given chemical in a given product. Where consumer skin exposure is low, a risk assessment can be conducted using the Dermal Sensitisation Threshold (DST) approach, avoiding the need to determine potency experimentally. Since skin sensitisation involves chemical reaction with skin proteins, the first step in the DST approach is to assess, on the basis of the chemical structure, whether the chemical is expected to be reactive or not. Our accompanying publication describes the probabilistic derivation of a DST of 64 μg/cm(2) for chemicals assessed as reactive. This would protect against 95% of chemicals assessed as reactive, but the remaining 5% would include chemicals with very high potency. Here we discuss the chemical properties and structural features of high potency sensitisers, and derive an approach whereby they can be identified and consequently excluded from application of the DST. Copyright © 2015 Elsevier Inc. All rights reserved.

Determining the Applicability of Threshold of Toxicological Concern Approaches to Substances Found in Foods

PubMed Central

Canady, Richard; Lane, Richard; Paoli, Greg; Wilson, Margaret; Bialk, Heidi; Hermansky, Steven; Kobielush, Brent; Lee, Ji-Eun; Llewellyn, Craig; Scimeca, Joseph

2013-01-01

Threshold of Toxicological Concern (TTC) decision-support methods present a pragmatic approach to using data from well-characterized chemicals and protective estimates of exposure in a stepwise fashion to inform decisions regarding low-level exposures to chemicals for which few data exist. It is based on structural and functional categorizations of chemicals derived from decades of animal testing with a wide variety of chemicals. Expertise is required to use the TTC methods, and there are situations in which its use is clearly inappropriate or not currently supported. To facilitate proper use of the TTC, this paper describes issues to be considered by risk managers when faced with the situation of an unexpected substance in food. Case studies are provided to illustrate the implementation of these considerations, demonstrating the steps taken in deciding whether it would be appropriate to apply the TTC approach in each case. By appropriately applying the methods, employing the appropriate scientific expertise, and combining use with the conservative assumptions embedded within the derivation of the thresholds, the TTC can realize its potential to protect public health and to contribute to efficient use of resources in food safety risk management. PMID:24090142

Investigation of electrophysical properties of allotropic modifications of carbon in the range of temperatures 140-400 K

NASA Astrophysics Data System (ADS)

Goshev, A. A.; Eseev, M. K.; Volkov, A. S.; Lyah, N. L.

2017-09-01

The paper presents the results of the investigation of allotropic modifications of carbon (coal, graphite, fullerenes, CNTs. Dependences of conductivity on the field frequency in the temperature range 140-400 K are presented. The characteristic features associated with the structure and types of hybridization are revealed. Calculation of the activation energy of carriers was performed. As well article presents experimental study of electrical properties of polymeric composites, reinforced different types of allotropic modifications of carbon (CNTs, graphite, fullerenes, coal) in alternating electrical field in frequency band from 0.01 Hz to 10 MHz. The threshold of percolation of polymer composites with various types of additives and their influence for conduction properties was estimated.

The use of new, aqueous chemical wood modifications to improve the durability of wood-plastic composites

Treesearch

Rebecca E. Ibach; Craig M. Clemons; George C. Chen

2017-01-01

The wood flour used in wood-plastic composites (WPCs) can biologically deteriorate and thus the overall mechanical performance of WPCs decrease when exposed to moisture and fungal decay. Protecting the wood flour by chemical modification can improve the durability of the wood in a nontoxic way so it is not harmful to the environment. WPCs were made with modified wood...

Chemical modification: the key to clinical application of RNA interference?

PubMed Central

Corey, David R.

2007-01-01

RNA interference provides a potent and specific method for controlling gene expression in human cells. To translate this potential into a broad new family of therapeutics, it is necessary to optimize the efficacy of the RNA-based drugs. As discussed in this Review, it might be possible to achieve this optimization using chemical modifications that improve their in vivo stability, cellular delivery, biodistribution, pharmacokinetics, potency, and specificity. PMID:18060019

Line length dependence of threshold current density and driving force in eutectic SnPb and SnAgCu solder electromigration

NASA Astrophysics Data System (ADS)

Yoon, Min-Seung; Ko, Min-Ku; Kim, Bit-Na; Kim, Byung-Joon; Park, Yong-Bae; Joo, Young-Chang

2008-04-01

The relationship between the threshold current density and the critical line length in eutectic SnPb and SnAgCu electromigrations were examined using solder lines with the various lengths ranging from 100to1000μm. When the electron wind-force was balanced by the back-stress gradient force, the net flux of electromigration is zero, at which the current density and line length are defined as the threshold current density and the critical length, respectively. It was found that in SnAgCu electromigration, the 1/L dependence on the threshold current density showed good agreement, whereas the threshold current densities of the eutectic SnPb deviated from the 1/L dependence. The balance between the electron wind-force and the back-stress gradient force was the main factor determining the threshold product of SnAgCu electromigration. On the other hand, in the case of eutectic SnPb, the chemical driving force is contributed as a back-flux force in addition to the back-stress gradient force. The existence of the chemical driving force was caused by the nonequilibrium Pb concentration inside the Pb-rich phases between the cathode and anode during the electromigration procedure.

Deamidation of Protonated Asparagine-Valine Investigated by a Combined Spectroscopic, Guided Ion Beam, and Theoretical Study.

PubMed

Kempkes, L J M; Boles, G C; Martens, J; Berden, G; Armentrout, P B; Oomens, J

2018-03-08

Peptide deamidation of asparaginyl residues is a spontaneous post-translational modification that is believed to play a role in aging and several diseases. It is also a well-known small-molecule loss channel in the MS/MS spectra of protonated peptides. Here we investigate the deamidation reaction, as well as other decomposition pathways, of the protonated dipeptide asparagine-valine ([AsnVal + H] + ) upon low-energy activation in a mass spectrometer. Using a combination of infrared ion spectroscopy, guided ion beam tandem mass spectrometry, and theoretical calculations, we have been able to identify product ion structures and determine the energetics and mechanisms for decomposition. Deamidation proceeds via ammonia loss from the asparagine side chain, initiated by a nucleophilic attack of the peptide bond oxygen on the γ-carbon of the Asn side chain. This leads to the formation of a furanone ring containing product ion characterized by a threshold energy of 129 ± 5 kJ/mol (15 kJ/mol higher in energy than dehydration of [AsnVal + H] + , the lowest energy dissociation channel available to the system). Competing formation of a succinimide ring containing product, as has been observed for protonated asparagine-glycine ([AsnGly + H] + ) and asparagine-alanine ([AsnAla + H] + ), was not observed here. Quantum-chemical modeling of the reaction pathways confirms these subtle differences in dissociation behavior. Measured reaction thresholds are in agreement with predicted theoretical reaction energies computed at several levels of theory.

Chemical Emergency Preparedness and Prevention Advisory: Ammonia

EPA Pesticide Factsheets

This advisory recommends ways Local Emergency Planning Committees (LEPCs) and chemical facilities can minimize risks from this extremely hazardous substance, especially when present in excess of its 500 pounds threshold planning quantity.

75 FR 26049 - Regulation of Fuels and Fuel Additives: Modifications to Renewable Fuel Standard Program

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-10

... conducted by ``a licensed professional engineer or foreign equivalent who works in the chemical engineering... chemical engineering field. EPA views renewable fuel production to fall generally within the chemical... basic organic chemical manufacturers. Industry 424690 5169 Chemical and allied products merchant...

Scaling of Precipitation Extremes Modelled by Generalized Pareto Distribution

NASA Astrophysics Data System (ADS)

Rajulapati, C. R.; Mujumdar, P. P.

2017-12-01

Precipitation extremes are often modelled with data from annual maximum series or peaks over threshold series. The Generalized Pareto Distribution (GPD) is commonly used to fit the peaks over threshold series. Scaling of precipitation extremes from larger time scales to smaller time scales when the extremes are modelled with the GPD is burdened with difficulties arising from varying thresholds for different durations. In this study, the scale invariance theory is used to develop a disaggregation model for precipitation extremes exceeding specified thresholds. A scaling relationship is developed for a range of thresholds obtained from a set of quantiles of non-zero precipitation of different durations. The GPD parameters and exceedance rate parameters are modelled by the Bayesian approach and the uncertainty in scaling exponent is quantified. A quantile based modification in the scaling relationship is proposed for obtaining the varying thresholds and exceedance rate parameters for shorter durations. The disaggregation model is applied to precipitation datasets of Berlin City, Germany and Bangalore City, India. From both the applications, it is observed that the uncertainty in the scaling exponent has a considerable effect on uncertainty in scaled parameters and return levels of shorter durations.

Recent Advances in Chemical Modification of Peptide Nucleic Acids

PubMed Central

Rozners, Eriks

2012-01-01

Peptide nucleic acid (PNA) has become an extremely powerful tool in chemistry and biology. Although PNA recognizes single-stranded nucleic acids with exceptionally high affinity and sequence selectivity, there is considerable ongoing effort to further improve properties of PNA for both fundamental science and practical applications. The present paper discusses selected recent studies that improve on cellular uptake and binding of PNA to double-stranded DNA and RNA. The focus is on chemical modifications of PNA's backbone and heterocyclic nucleobases. The paper selects representative recent studies and does not attempt to provide comprehensive coverage of the broad and vibrant field of PNA modification. PMID:22991652

Functionalization of chitosan by click chemistry

NASA Astrophysics Data System (ADS)

Cheaburu-Yilmaz, Catalina Natalia; Karavana, Sinem Yaprak; Yilmaz, Onur

2017-12-01

Chitosan modification represents a challenge nowadays. The variety of compounds which can be obtained with various architectures and different functionalities made it attractive to be used in fields like pharmacy and material science. Presents study deals with the chemical modification of chitosan by using click chemistry technique. The study adopted the approach of clicking azidated chitosan with a synthesized alkyne terminated polymer i.e. poly N isopropylacrylamide with thermoresponsive properties. Structures were confirmed by the FT-IR and HNMR spectra. Thermal characterization was performed showing different thermal behaviour with the chemical modification. The final synthesized graft copolymer can play important role within pharmaceutical formulations carrying drugs for topical or oral treatments.

RMP Guidance for Chemical Distributors - Appendix A: 40 CFR part 68/Selected NAICS Codes

EPA Pesticide Factsheets

The full text of Part 68, Chemical Accident Prevention provisions, includes hazard assessment, emergency response, threshold quantities for regulated substances, reporting requirements, and the Risk Management Plan.

Observed physical processes in mechanical tests of PBX9501 and recomendations for experiments to explore a possible plasticity/damage threshold

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buechler, Miles A.

2012-05-02

This memo discusses observations that have been made in regards to a series of monotonic and cyclic uniaxial experiments performed on PBX9501 by Darla Thompson under Enhanced Surveilance Campaign support. These observations discussed in Section Cyclic compression observations strongly suggest the presence of viscoelastic, plastic, and damage phenomena in the mechanical response of the material. In Secton Uniaxial data analysis and observations methods are discussed for separating out the viscoelastic effects. A crude application of those methods suggests the possibility of a critical stress below which plasticity and damage may be negligible. The threshold should be explored because if itmore » exists it will be an important feature of any constitutive model. Additionally, if the threshold exists then modifications of experimental methods may be feasible which could potentially simplify future experiments or provide higher quality data from those experiments. A set of experiments to explore the threshold stress are proposed in Section Exploratory tests program for identifying threshold stress.« less

Influence of major-groove chemical modifications of DNA on transcription by bacterial RNA polymerases.

PubMed

Raindlová, Veronika; Janoušková, Martina; Slavíčková, Michaela; Perlíková, Pavla; Boháčová, Soňa; Milisavljevič, Nemanja; Šanderová, Hana; Benda, Martin; Barvík, Ivan; Krásný, Libor; Hocek, Michal

2016-04-20

DNA templates containing a set of base modifications in the major groove (5-substituted pyrimidines or 7-substituted 7-deazapurines bearing H, methyl, vinyl, ethynyl or phenyl groups) were prepared by PCR using the corresponding base-modified 2'-deoxyribonucleoside triphosphates (dNTPs). The modified templates were used in an in vitro transcription assay using RNA polymerase from Bacillus subtilis and Escherichia coli Some modified nucleobases bearing smaller modifications (H, Me in 7-deazapurines) were perfectly tolerated by both enzymes, whereas bulky modifications (Ph at any nucleobase) and, surprisingly, uracil blocked transcription. Some middle-sized modifications (vinyl or ethynyl) were partly tolerated mostly by the E. colienzyme. In all cases where the transcription proceeded, full length RNA product with correct sequence was obtained indicating that the modifications of the template are not mutagenic and the inhibition is probably at the stage of initiation. The results are promising for the development of bioorthogonal reactions for artificial chemical switching of the transcription. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

Base modifications affecting RNA polymerase and reverse transcriptase fidelity.

PubMed

Potapov, Vladimir; Fu, Xiaoqing; Dai, Nan; Corrêa, Ivan R; Tanner, Nathan A; Ong, Jennifer L

2018-06-20

Ribonucleic acid (RNA) is capable of hosting a variety of chemically diverse modifications, in both naturally-occurring post-transcriptional modifications and artificial chemical modifications used to expand the functionality of RNA. However, few studies have addressed how base modifications affect RNA polymerase and reverse transcriptase activity and fidelity. Here, we describe the fidelity of RNA synthesis and reverse transcription of modified ribonucleotides using an assay based on Pacific Biosciences Single Molecule Real-Time sequencing. Several modified bases, including methylated (m6A, m5C and m5U), hydroxymethylated (hm5U) and isomeric bases (pseudouridine), were examined. By comparing each modified base to the equivalent unmodified RNA base, we can determine how the modification affected cumulative RNA polymerase and reverse transcriptase fidelity. 5-hydroxymethyluridine and N6-methyladenosine both increased the combined error rate of T7 RNA polymerase and reverse transcriptases, while pseudouridine specifically increased the error rate of RNA synthesis by T7 RNA polymerase. In addition, we examined the frequency, mutational spectrum and sequence context of reverse transcription errors on DNA templates from an analysis of second strand DNA synthesis.

It is time to develop ecological thresholds of toxicological concern to assist environmental hazard assessment.

PubMed

Belanger, Scott E; Sanderson, Hans; Embry, Michelle R; Coady, Katie; DeZwart, Dick; Farr, Brianna A; Gutsell, Steve; Halder, Marlies; Sternberg, Robin; Wilson, Peter

2015-12-01

The threshold of toxicological concern (TTC) concept is well established for assessing human safety of food-contact substances and has been reapplied for a variety of endpoints, including carcinogenicity, teratogenicity, and reproductive toxicity. The TTC establishes an exposure level for chemicals below which no appreciable risk to human health or the environment is expected, based on a de minimis value for toxicity identified for many chemicals. Threshold of toxicological concern approaches have benefits for screening-level risk assessments, including the potential for rapid decision-making, fully utilizing existing knowledge, reasonable conservativeness for chemicals used in lower volumes (low production volume chemicals (e.g., < 1 t/yr), and reduction or elimination of unnecessary animal tests. Higher production volume chemicals (>1 t/yr) would in principle always require specific information because of the presumed higher exposure potential. The TTC approach has found particular favor in the assessment of chemicals used in cosmetics and personal care products, as well as other chemicals traditionally used in low volumes. Use of the TTC in environmental safety is just beginning, and initial attempts are being published. Key questions focus on hazard extrapolation of diverse taxa across trophic levels, importance of mode of action, and whether safe concentrations for ecosystems estimated from acute or chronic toxicity data are equally useful and in what contexts. The present study provides an overview of the theoretical basis for developing an ecological (eco)-TTC, with an initial exploration of chemical assessment and boundary conditions for use. An international collaboration under the International Life Sciences Institute Health and Environmental Sciences Institute has been established to address challenges related to developing and applying useful eco-TTC concepts. © 2015 SETAC.

Effect of two doses of carbamylated allergoid extract of dust mite on nasal reactivity.

PubMed

Scalone, G; Compalati, E; Bruno, M E; Mistrello, G

2013-11-01

Background and Objective. Single SLIT studies with native allergen extracts support a dose-response effect for clinical and immunological outcomes. Conversely for carbamylated allergoids this dose-response effects is less evident, likely because the threshold for efficacy is more easily reached through the enhanced bioavailability of the extract consequent to the selective chemical modification. Thus this pilot study investigates the dose-response effect on nasal specific reactivity and safety of two unusual doses of carbamylated allergoid in patients mono-sensitized to house dust mites. Methods. A prospective open randomized study involved 6-65 year-old Italian patients with clinically relevant sensitization to house dust mites and positive response to nasal provocation challenge. Monomeric carbamylated allergoid was delivered once daily at the dose of 1000 AU or 2000 AU from June to September 2009, during the lowest level of mites exposure. Primary outcomes were the change of the threshold of allergen concentration for a positive nasal provocation test (NPT) before and after the treatment and the product safety. Secondary outcome was the change  in the mean percentage fall of peak nasal inspiratory flow (PNIF) following nasal challenge. Results. Thirty-four patients were enrolled. Fifteen in group 1 and 14 in group 2 concluded the study. After 12 weeks all patients treated in group 1 and all but one in group 2 showed an increase in the threshold dose provoking a positive NPT. Those with no symptoms onset with the highest dose delivered were 80% in group 1 and 78.6% in group 2 (p=0.92). From first to second challenge, the mean percentage fall of PNIF  was reduced with no statistical difference between groups (p=0.95), and with no difference between the final mean percentage falls (p=0.65). No serious adverse reactions occurred and the frequency of events, all mild, was similar in the two groups. Conclusions. Twelve weeks of carbamylated sublingual allergoid delivered at 1000AU or 2000AU once daily appear equally safe and show comparable effect in increasing  the threshold of allergen concentration for a positive nasal provocation test, confirming the apparent absence of a dose response effect for the used doses.

Genetic engineering and chemical conjugation of potato virus X.

PubMed

Lee, Karin L; Uhde-Holzem, Kerstin; Fischer, Rainer; Commandeur, Ulrich; Steinmetz, Nicole F

2014-01-01

Here we report the genetic engineering and chemical modification of potato virus X (PVX) for the presentation of various peptides, proteins, and fluorescent dyes, or other chemical modifiers. Three different ways of genetic engineering are described and by these means, peptides are successfully expressed not only when the foot and mouth disease virus (FMDV) 2A sequence or a flexible glycine-serine linker is included, but also when the peptide is fused directly to the PVX coat protein. When larger proteins or unfavorable peptide sequences are presented, a partial fusion via the FMDV 2A sequence is preferable. When these PVX chimeras retain the ability to assemble into viral particles and are thus able to infect plants systemically, they can be utilized to inoculate susceptible plants for isolation of sufficient amounts of virus particles for subsequent chemical modification. Chemical modification is required for the display of nonbiological ligands such as fluorophores, polymers, and small drug compounds. We present three methods of chemical bioconjugation. For direct conjugation of small chemical modifiers to solvent exposed lysines, N-hydroxysuccinimide chemistry can be applied. Bio-orthogonal reactions such as copper-catalyzed azide-alkyne cycloaddition or hydrazone ligation are alternatives to achieve more efficient conjugation (e.g., when working with high molecular weight or insoluble ligands). Furthermore, hydrazone ligation offers an attractive route for the introduction of pH-cleavable cargos (e.g., therapeutic molecules).

Causes of genome instability: the effect of low dose chemical exposures in modern society

PubMed Central

Langie, Sabine A.S.; Koppen, Gudrun; Desaulniers, Daniel; Al-Mulla, Fahd; Al-Temaimi, Rabeah; Amedei, Amedeo; Azqueta, Amaya; Bisson, William H.; Brown, Dustin; Brunborg, Gunnar; Charles, Amelia K.; Chen, Tao; Colacci, Annamaria; Darroudi, Firouz; Forte, Stefano; Gonzalez, Laetitia; Hamid, Roslida A.; Knudsen, Lisbeth E.; Leyns, Luc; Lopez de Cerain Salsamendi, Adela; Memeo, Lorenzo; Mondello, Chiara; Mothersill, Carmel; Olsen, Ann-Karin; Pavanello, Sofia; Raju, Jayadev; Rojas, Emilio; Roy, Rabindra; Ryan, Elizabeth; Ostrosky-Wegman, Patricia; Salem, Hosni K.; Scovassi, Ivana; Singh, Neetu; Vaccari, Monica; Van Schooten, Frederik J.; Valverde, Mahara; Woodrick, Jordan; Zhang, Luoping; van Larebeke, Nik; Kirsch-Volders, Micheline; Collins, Andrew R.

2015-01-01

Genome instability is a prerequisite for the development of cancer. It occurs when genome maintenance systems fail to safeguard the genome’s integrity, whether as a consequence of inherited defects or induced via exposure to environmental agents (chemicals, biological agents and radiation). Thus, genome instability can be defined as an enhanced tendency for the genome to acquire mutations; ranging from changes to the nucleotide sequence to chromosomal gain, rearrangements or loss. This review raises the hypothesis that in addition to known human carcinogens, exposure to low dose of other chemicals present in our modern society could contribute to carcinogenesis by indirectly affecting genome stability. The selected chemicals with their mechanisms of action proposed to indirectly contribute to genome instability are: heavy metals (DNA repair, epigenetic modification, DNA damage signaling, telomere length), acrylamide (DNA repair, chromosome segregation), bisphenol A (epigenetic modification, DNA damage signaling, mitochondrial function, chromosome segregation), benomyl (chromosome segregation), quinones (epigenetic modification) and nano-sized particles (epigenetic pathways, mitochondrial function, chromosome segregation, telomere length). The purpose of this review is to describe the crucial aspects of genome instability, to outline the ways in which environmental chemicals can affect this cancer hallmark and to identify candidate chemicals for further study. The overall aim is to make scientists aware of the increasing need to unravel the underlying mechanisms via which chemicals at low doses can induce genome instability and thus promote carcinogenesis. PMID:26106144

75 FR 78798 - Airport Improvement Program: Proposed Changes to Benefit Cost Analysis (BCA) Threshold

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-16

...The Federal Aviation Administration (FAA) is issuing this Notice to advise that FAA has developed draft guidance modifying its policy requiring benefit cost analyses (BCA) for capacity projects when applying for Airport Improvement Program (AIP) grants for capacity projects at the discretion of the Secretary of Transportation. This modification proposes to raise the threshold at which BCAs are required, from $5 million to $10 million in AIP Discretionary funds. FAA invites airport sponsors and other interested parties to comment on the draft guidance. FAA will consider these comments in promulgating final BCA guidance for airport sponsors.

Chemical synthesis of membrane proteins by the removable backbone modification method.

PubMed

Tang, Shan; Zuo, Chao; Huang, Dong-Liang; Cai, Xiao-Ying; Zhang, Long-Hua; Tian, Chang-Lin; Zheng, Ji-Shen; Liu, Lei

2017-12-01

Chemical synthesis can produce membrane proteins bearing specifically designed modifications (e.g., phosphorylation, isotope labeling) that are difficult to obtain through recombinant protein expression approaches. The resulting homogeneously modified synthetic membrane proteins are valuable tools for many advanced biochemical and biophysical studies. This protocol describes the chemical synthesis of membrane proteins by condensation of transmembrane peptide segments through native chemical ligation. To avoid common problems encountered due to the poor solubility of transmembrane peptides in almost any solvent, we describe an effective procedure for the chemical synthesis of membrane proteins through the removable-backbone modification (RBM) strategy. Two key steps of this protocol are: (i) installation of solubilizing Arg4-tagged RBM groups into the transmembrane peptides at any primary amino acid through Fmoc (9-fluorenylmethyloxycarbonyl) solid-phase peptide synthesis and (ii) native ligation of the full-length sequence, followed by removal of the RBM tags by TFA (trifluoroacetic acid) cocktails to afford the native protein. The installation of RBM groups is achieved by using 4-methoxy-5-nitrosalicyladehyde by reduction amination to incorporate an activated O-to-N acyl transfer auxiliary. The Arg4-tag-modified membrane-spanning peptide segments behave like water-soluble peptides to facilitate their purification, ligation and mass characterization.

Chemically Modified Polyvinyl Chloride for Removal of Thionine Dye (Lauth’s Violet)

PubMed Central

Silva, Cleuzilene V.; Royer, Betina; Rodrigues Filho, Guimes; Cerqueira, Daniel A.; Assunção, Rosana M. N.

2017-01-01

The chemical modification of hydrophobic polymer matrices is an alternative way to elchange their surface properties. The introduction of sulfonic groups in the polymer changes the surface properties such as adhesion, wettability, catalytic ability, and adsorption capacity. This work describes the production and application of chemically modified polyvinyl chloride (PVC) as adsorbent for dyes removal. Chemical modification of PVC was evaluated by infrared spectroscopy and elemental analysis, which indicated the presence of sulfonic groups on PVC. The chemically modified PVC (PVCDS) showed an ion exchange capacity of 1.03 mmol−1, and efficiently removed the thionine dye (Lauth’s violet) from aqueous solutions, reaching equilibrium in 30 min. The adsorption kinetics was better adjusted for a pseudo second order model. This result indicates that the adsorption of thionine onto PVCDS occurs by chemisorption. Among the models for the state of equilibrium, SIPS and Langmuir exhibited the best fit to the experimental results and PVCDS showed high adsorption capacities (370 mg−1). Thus, it is assumed that the system presents homogeneous characteristics to the distribution of active sites. The modification promoted the formation of surface characteristics favorable to the dye adsorption by the polymer. PMID:29137158

Stability in the Social Percolation Models for Two to Four Dimensions

NASA Astrophysics Data System (ADS)

Huang, Zhi-Feng

The social percolation model proposed by Solomon et al. as well as its modification are studied in two to four dimensions for the phenomena of self-organized criticality. Stability in the models is obtained and the systems are shown to automatically drift towards the percolation threshold.

76 FR 81836 - Approval and Promulgation of Air Quality Implementation Plans; New Mexico; Albuquerque/Bernalillo...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-29

... Significant Deterioration (PSD) program to establish appropriate emission thresholds for determining which new stationary sources and modification projects become subject to Albuquerque/Bernalillo County's PSD permitting..., New Mexico December 15, 2010 PSD SIP revision because the Agency has determined that this PSD SIP...

77 FR 11744 - Approval and Promulgation of Implementation Plans; Tennessee: Prevention of Significant...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-28

... New Source Review (NSR) Prevention of Significant Deterioration (PSD) program. Specifically, the SIP... modification projects become subject to Tennessee's PSD permitting requirements for GHG emissions. This rule... thresholds in the Tennessee SIP for GHG PSD requirements. EPA is approving Tennessee's January 11, 2012, SIP...

75 FR 81863 - Approval and Promulgation of Implementation Plans; Alabama: Prevention of Significant...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-29

... Deterioration (PSD) program. Specifically, the SIP revision establishes appropriate emission thresholds for determining which new stationary sources and modification projects become subject to Alabama's PSD permitting requirements for their GHG emissions. The change is necessary because without it, on January 2, 2011, PSD...

Plant Sterols: Chemical and Enzymatic Structural Modifications and Effects on Their Cholesterol-Lowering Activity.

PubMed

He, Wen-Sen; Zhu, Hanyue; Chen, Zhen-Yu

2018-03-28

Plant sterols have attracted increasing attention due to their excellent cholesterol-lowering activity. However, free plant sterols have some characteristics of low oil solubility, water insolubility, high melting point, and low bioavailability, which greatly limit their application in foods. Numerous studies have been undertaken to modify their chemical structures to improve their chemical and physical properties in meeting the needs of various applications. The present review is to summarize the literature and update the progress on structural modifications of plant sterols in the following aspects: (i) synthesis of plant sterol esters by esterification and transesterification with hydrophobic fatty acids and triacylglycerols to improve their oil solubility, (ii) synthesis of plant sterol derivatives by coupling with various hydrophilic moieties to enhance their water solubility, and (iii) mechanisms by which plant sterols reduce plasma cholesterol and the effect of structural modifications on plasma cholesterol-lowering activity of plant sterols.

Modification of chemical reactivity of enzymatic hydrolysis lignin by ultrasound treatment in dilute alkaline solutions.

PubMed

Ma, Zhuoming; Li, Shujun; Fang, Guizhen; Patil, Nikhil; Yan, Ning

2016-12-01

In this study, we have explored various ultrasound treatment conditions for structural modification of enzymatic hydrolysis lignin (EHL) for enhanced chemical reactivity. The key structural modifications were characterized by using a combination of analytical methods, including, Fourier Transform-Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance ( 1 H NMR), Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Folin-Ciocalteu (F-C) method. Chemical reactivity of the modified EHL samples was determined by both 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and their reactivity towards formaldehyde. It was observed that the modified EHL had a higher phenolic hydroxyl group content, a lower molecular weight, a higher reactivity towards formaldehyde, and a greater antioxidant property. The higher reactivity demonstrated by the samples after treatment suggesting that ultrasound is a promising method for modifying enzymatic hydrolysis lignin for value-added applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Design and Control of Chemical Grouting : Volume 3 - Engineering Practice

DOT National Transportation Integrated Search

1983-04-01

Recent improvements in the engineering practice of chemical grouting have provided increased confidence in this method of ground modification. Designers can significantly improve the success of chemical grouting by defining their grouting program obj...

Chemical Data Reporting - Previously Collected Data

EPA Pesticide Factsheets

EPA now refers to the Inventory Update Reporting (IUR) rule as the Chemical Data Reporting (CDR) Rule. This change was effective with the publication of the Inventory Update Reporting Modifications; Chemical Data Reporting Final Rule in August 2011.

Non-aqueous homogenous biocatalytic conversion of polysaccharides in ionic liquids using chemically modified glucosidase.

PubMed

Brogan, Alex P S; Bui-Le, Liem; Hallett, Jason P

2018-06-25

The increasing requirement to produce platform chemicals and fuels from renewable sources means advances in biocatalysis are rapidly becoming a necessity. Biomass is widely used in nature as a source of energy and as chemical building blocks. However, recalcitrance towards traditional chemical processes and solvents provides a significant barrier to widespread utility. Here, by optimizing enzyme solubility in ionic liquids, we have discovered solvent-induced substrate promiscuity of glucosidase, demonstrating an unprecedented example of homogeneous enzyme bioprocessing of cellulose. Specifically, chemical modification of glucosidase for solubilization in ionic liquids can increase thermal stability to up to 137 °C, allowing for enzymatic activity 30 times greater than is possible in aqueous media. These results establish that through a synergistic combination of chemical biology (enzyme modification) and reaction engineering (solvent choice), the biocatalytic capability of enzymes can be intensified: a key step towards the full-scale deployment of industrial biocatalysis.

Dose Response Data for Hormonally Active Chemicals: Estrogens, Antiandrogens and Androgens

EPA Science Inventory

The shape of the dose response curve in the low dose region has been debated since the late 1940s. The debate originally focused on linear no threshold (LNT) vs threshold responses in the low dose range for cancer and noncancer related effects. For noncancer effects the defaul...

40 CFR 372.27 - Alternate threshold and certification.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 28 2014-07-01 2014-07-01 false Alternate threshold and certification. 372.27 Section 372.27 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Reporting Requirements § 372.2...

40 CFR 372.95 - Alternate threshold certification and instructions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 29 2012-07-01 2012-07-01 false Alternate threshold certification and instructions. 372.95 Section 372.95 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Forms and...

40 CFR 372.27 - Alternate threshold and certification.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 29 2012-07-01 2012-07-01 false Alternate threshold and certification. 372.27 Section 372.27 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Reporting Requirements § 372.2...

40 CFR 372.27 - Alternate threshold and certification.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 27 2010-07-01 2010-07-01 false Alternate threshold and certification. 372.27 Section 372.27 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Reporting Requirements § 372.2...

40 CFR 372.95 - Alternate threshold certification and instructions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 28 2014-07-01 2014-07-01 false Alternate threshold certification and instructions. 372.95 Section 372.95 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Forms and...

40 CFR 372.27 - Alternate threshold and certification.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 28 2011-07-01 2011-07-01 false Alternate threshold and certification. 372.27 Section 372.27 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Reporting Requirements § 372.2...

40 CFR 372.95 - Alternate threshold certification and instructions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 28 2011-07-01 2011-07-01 false Alternate threshold certification and instructions. 372.95 Section 372.95 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Forms and...

40 CFR 372.95 - Alternate threshold certification and instructions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 27 2010-07-01 2010-07-01 false Alternate threshold certification and instructions. 372.95 Section 372.95 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SUPERFUND, EMERGENCY PLANNING, AND COMMUNITY RIGHT-TO-KNOW PROGRAMS TOXIC CHEMICAL RELEASE REPORTING: COMMUNITY RIGHT-TO-KNOW Forms and...

The simulation of electromagnetically driven strong Langmuir turbulence effect on the backscatter radiation from ionosphere

NASA Astrophysics Data System (ADS)

Kochetov, Andrey

2016-07-01

Numerical simulations of the dynamics of electromagnetic fields in a smoothly inhomogeneous nonlinear plasma layer in frameworks of the nonlinear Schrödinger equation with boundary conditions responsible for the pumping of the field in the layer by an incident wave and the inverse radiation losses supplemented the volume field dissipation due to the electromagnetic excitation of Langmuir turbulence are carried out. The effects of the threshold of non-linearity and it's evolution, of the threshold and saturation levels of dissipation in the vicinity of the wave reflection point on the features of the dynamics of reflection and absorption indexes are investigated. We consider the hard drive damping depending on the local field amplitude and hysteresis losses with different in several times "on" and "off" absorption thresholds as well. The dependence of the thresholds of the steady-state, periodic and chaotic regimes of plasma-wave interaction on the scenario of turbulence evolution is demonstrated. The results are compared with the experimental observations of Langmuir stage ionospheric modification.

Threshold corrections to the bottom quark mass revisited

DOE PAGES

Anandakrishnan, Archana; Bryant, B. Charles; Raby, Stuart

2015-05-19

Threshold corrections to the bottom quark mass are often estimated under the approximation that tan β enhanced contributions are the most dominant. In this work we revisit this common approximation made to the estimation of the supersymmetric thresh-old corrections to the bottom quark mass. We calculate the full one-loop supersymmetric corrections to the bottom quark mass and survey a large part of the phenomenological MSSM parameter space to study the validity of considering only the tan β enhanced corrections. Our analysis demonstrates that this approximation underestimates the size of the threshold corrections by ~12.5% for most of the considered parametermore » space. We discuss the consequences for fitting the bottom quark mass and for the effective couplings to Higgses. Here, we find that it is important to consider the additional contributions when fitting the bottom quark mass but the modifications to the effective Higgs couplings are typically O(few)% for the majority of the parameter space considered.« less

15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

Code of Federal Regulations, 2013 CFR

2013-01-01

... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared...; (iii) You plan to increase the production of a Schedule 3 chemical by declared plants on your plant... production of a Schedule 3 chemical at a declared plant site to an amount above the upper limit of the range...

15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

Code of Federal Regulations, 2012 CFR

2012-01-01

... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared...; (iii) You plan to increase the production of a Schedule 3 chemical by declared plants on your plant... production of a Schedule 3 chemical at a declared plant site to an amount above the upper limit of the range...

15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

Code of Federal Regulations, 2014 CFR

2014-01-01

... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared...; (iii) You plan to increase the production of a Schedule 3 chemical by declared plants on your plant... production of a Schedule 3 chemical at a declared plant site to an amount above the upper limit of the range...

15 CFR Supplement No. 2 to Part 714 - Deadlines for Submission of Schedule 3 Declarations, Reports, and Amendments

Code of Federal Regulations, 2011 CFR

2011-01-01

... CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS Pt. 714, Supp. 2... Schedule 3 chemical exceeded the declaration threshold in § 714.1(a)(1)(i) of the CWCR. Annual Report on... year in which exports or imports of a Schedule 3 chemical by a plant site, trading company, or other...

Chemical modification of cellulose-rich fibres to clarify the influence of the chemical structure on the physical and mechanical properties of cellulose fibres and thereof made sheets.

PubMed

López Durán, Verónica; Larsson, Per A; Wågberg, Lars

2018-02-15

Despite the different chemical approaches used earlier to increase the ductility of fibre-based materials, it has not been possible to link the chemical modification to their mechanical performance. In this study, cellulose fibres have been modified by periodate oxidation, alone or followed either by borohydride reduction, reductive amination or chlorite oxidation. In addition, TEMPO oxidation, and TEMPO oxidation in combination with periodate oxidation and further reduction with sodium borohydride have also been studied. The objective was to gain understanding of the influence of different functional groups on the mechanical and structural properties of handsheets made from the modified fibres. It was found that the modifications studied improved the tensile strength of the fibres to different extents, but that only periodate oxidation followed by borohydride reduction provided more ductile fibre materials. Changes in density, water-holding capacity and mechanical performance were also quantified and all are dependent on the functional group introduced. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of modified titanium surfaces physical and chemical characteristics

NASA Astrophysics Data System (ADS)

Lukaszewska-Kuska, Magdalena; Leda, Bartosz; Gajdus, Przemyslaw; Hedzelek, Wieslaw

2017-11-01

Development of dental implantology is focused, among other things, on devising active surface of the implant, conditioning acceleration of the implant's integration with the bone. Increased roughness, characteristic for group of implants with developed surface, altered topography and chemically modified implant's surface determines increased implants stability. In this study four different titanium surfaces modifications: turned (TS); aluminium oxide-blasted (Al2O3); resorbable material blasted (RBM); sandblast and then etched with a mixture of acids (SAE), were evaluated in terms of surfaces topography and chemical composition prior to in vivo analysis. Topography analysis revealed two groups: one with smooth, anisotropic, undeveloped TS surface and the second group with remaining surfaces presenting rough, isotropic, developed surfaces with added during blasting procedure aluminium for Al2O3 and calcium and phosphorus for RBM. Physical and chemical modifications of titanium surface change its microstructure (typical for SAE) and increase its roughness (highest for Al2O3-blasted and RBM surfaces). The introduced modifications develop titanium surface - 10 times for SAE surfaces, 16 times for Al2O3-blasted surfaces, and 20 times for RBM surfaces.

Experimental and quantum chemical studies on Nsbnd Hsbnd sbnd sbnd O hydrogen bonded helical chain type Morpholinium 2-chloro-4-nitrobenzoate: A phasematchable organic nonlinear optical material

NASA Astrophysics Data System (ADS)

Karthick, S.; Thirupugalmani, K.; Shanmugam, G.; Kannan, V.; Brahadeeswaran, S.

2018-03-01

We report on the studies performed on Morpholinium 2-chloro-4-nitrobenzoate (M2C4N), a second order nonlinear optical (NLO) material, which has been proved to crystallize with chiral structure as compared to its other two variants. The synthesized powder was studied for its composition, crystalline phase and NLO efficiency and phasematchability. The solubility and the metastable zone width (MSZW) of the title compound were measured for the growth of bulk crystals of M2C4N. A smoky pattern observed in the middle region of the crystals that could prevent it from optical applications was greatly reduced, through suitable modifications in the growth process. The optical properties such as luminescence and laser damage threshold resistance were studied for the bulk crystals whereas the molecular vibrations of M2C4N were studied through Fourier transform infrared (FTIR) and FT-Raman spectral analysis using the polycrystalline powders derived from the single crystals. In addition, quantum chemical studies on M2C4N molecule were performed by using density functional theory (DFT) at the B3LYP/6-311++G (d, p) basis set. These studies showed that the M2C4N is a phasematchable NLO crystal and could be used for device fabrication.

Identification and characterization of ana o 3 modifications on arginine-111 residue in heated cashew nuts

USDA-ARS?s Scientific Manuscript database

Heating foods can alter the physical, chemical, and biological characteristics of the proteins we consume. Raw and roasted cashew nut extracts were evaluated for allergen modifications by mass-spectrometry. We did not identify modifications on Ana o 1 or Ana o 2, but we observed two independent mo...

Estimation of risks by chemicals produced during laser pyrolysis of tissues

NASA Astrophysics Data System (ADS)

Weber, Lothar W.; Spleiss, Martin

1995-01-01

Use of laser systems in minimal invasive surgery results in formation of laser aerosol with volatile organic compounds of possible health risk. By use of currently identified chemical substances an overview on possibly associated risks to human health is given. The class of the different identified alkylnitriles seem to be a laser specific toxicological problem. Other groups of chemicals belong to the Maillard reaction type, the fatty acid pyrolysis type, or even the thermally activated chemolysis. In relation to the available different threshold limit values the possible exposure ranges of identified substances are discussed. A rough estimation results in an exposure range of less than 1/100 for almost all substances with given human threshold limit values without regard of possible interactions. For most identified alkylnitriles, alkenes, and heterocycles no threshold limit values are given for lack of, until now, practical purposes. Pyrolysis of anaesthetized organs with isoflurane gave no hints for additional pyrolysis products by fragment interactions with resulting VOCs. Measurements of pyrolysis gases resulted in detection of small amounts of NO additionally with NO2 formation at plasma status.

A covalent modification for graphene by adamantane groups through two-step chlorination-Grignard reactions

NASA Astrophysics Data System (ADS)

Sun, Xuzhuo; Li, Bo; Lu, Mingxia

2017-07-01

Chemical modification of graphene is a promising approach to manipulate its properties for its end applications. Herein we designed a two-step route through chlorination-Grignard reactions to covalently decorate the surface of graphene with adamantane groups. The chemically modified graphene was characterized by Raman spectroscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Chlorination of graphene occurred rapidly, and the substitution of chlorine atoms on chlorinated graphene by adamantane Grignard reagent afforded adamantane graphene in almost quantitative yield. Adamantane groups were found to be covalently bonded to the graphene carbons. The present two-step procedure may provide an effective and facile route for graphene modification with varieties of organic functional groups.

Effect of water treatment additives on lime softening residual trace chemical composition--implications for disposal and reuse.

PubMed

Cheng, Weizhi; Roessler, Justin; Blaisi, Nawaf I; Townsend, Timothy G

2014-12-01

Drinking water treatment residues (WTR) offer potential benefits when recycled through land application. The current guidance in Florida, US allows for unrestricted land application of lime softening WTR; alum and ferric WTR require additional evaluation of total and leachable concentrations of select trace metals prior to land application. In some cases a mixed WTR is produced when lime softening is accompanied by the addition of a coagulant or other treatment chemical; applicability of the current guidance is unclear. The objective of this research was to characterize the total and leachable chemical content of WTR from Florida facilities that utilize multiple treatment chemicals. Lime and mixed lime WTR samples were collected from 18 water treatment facilities in Florida. Total and leachable concentrations of the WTR were measured. To assess the potential for disposal of mixed WTR as clean fill below the water table, leaching tests were conducted at multiple liquid to solid ratios and under reducing conditions. The results were compared to risk-based soil and groundwater contamination thresholds. Total metal concentrations of WTR were found to be below Florida soil contaminant thresholds with Fe found in the highest abundance at a concentration of 3600 mg/kg-dry. Aluminum was the only element that exceeded the Florida groundwater contaminant thresholds using SPLP (95% UCL = 0.23 mg/L; risk threshold = 0.2 mg/L). Tests under reducing conditions showed elevated concentrations of Fe and Mn, ranging from 1 to 3 orders of magnitude higher than SPLP leachates. Mixed lime WTR concentrations (total and leachable) were lower than the ferric and alum WTR concentrations, supporting that mixed WTR are appropriately represented as lime WTR. Testing of WTR under reducing conditions demonstrated the potential for release of certain trace metals (Fe, Al, Mn) above applicable regulatory thresholds; additional evaluation is needed to assess management options where reducing conditions may develop. Copyright © 2014 Elsevier Ltd. All rights reserved.

Acceptance threshold hypothesis is supported by chemical similarity of cuticular hydrocarbons in a stingless bee, Melipona asilvai.

PubMed

Nascimento, D L; Nascimento, F S

2012-11-01

The ability to discriminate nestmates from non-nestmates in insect societies is essential to protect colonies from conspecific invaders. The acceptance threshold hypothesis predicts that organisms whose recognition systems classify recipients without errors should optimize the balance between acceptance and rejection. In this process, cuticular hydrocarbons play an important role as cues of recognition in social insects. The aims of this study were to determine whether guards exhibit a restrictive level of rejection towards chemically distinct individuals, becoming more permissive during the encounters with either nestmate or non-nestmate individuals bearing chemically similar profiles. The study demonstrates that Melipona asilvai (Hymenoptera: Apidae: Meliponini) guards exhibit a flexible system of nestmate recognition according to the degree of chemical similarity between the incoming forager and its own cuticular hydrocarbons profile. Guards became less restrictive in their acceptance rates when they encounter non-nestmates with highly similar chemical profiles, which they probably mistake for nestmates, hence broadening their acceptance level.

A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

PubMed

Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

2016-09-21

Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

Drug development and manufacturing

DOEpatents

Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

2015-10-13

X-ray fluorescence (XRF) spectrometry has been used for detecting binding events and measuring binding selectivities between chemicals and receptors. XRF may also be used for estimating the therapeutic index of a chemical, for estimating the binding selectivity of a chemical versus chemical analogs, for measuring post-translational modifications of proteins, and for drug manufacturing.

Response of genioglossus muscle to increasing chemical drive in sleeping obstructive apnea patients.

PubMed

Loewen, Andrea H S; Ostrowski, Michele; Laprairie, John; Maturino, Frances; Hanly, Patrick J; Younes, Magdy

2011-08-01

Subjects with a collapsible upper airway must activate their pharyngeal dilators sufficiently in response to increasing chemical drive if they are to maintain airway patency without arousal from sleep. Little is known about the response of pharyngeal dilators to increasing chemical drive in these subjects. We wished to determine, in obstructive apnea patients, the response of the genioglossus to increasing chemical drive and the contribution of mechanoreceptor feedback to this response. Physiological study. University-based sleep laboratory. 20 patients with obstructive apnea. Genioglossus activity was monitored during overnight polysomnography on optimal continuous positive airway pressure (CPAP). Intermittently, inspired gases were altered to produce different levels of ventilatory stimulation. CPAP was then briefly reduced to 1.0 cm H(2)O (dial-down), inducing an obstruction. Without mechanoreceptor feedback (i.e., on CPAP) the increase in genioglossus activity as ventilation increased from 6.1 ± 1.4 to 16.1 ± 4.8 L/min was modest (ΔTonic activity 0.3% ± 0.5%maximum; ΔPhasic activity 1.7% ± 3.4%maximum). Genioglossus activity increased immediately upon dial-down, reflecting mechanoreceptor feedback, but only when ventilation before dial-down exceeded a threshold value. This threshold varied among patients and, once surpassed, genioglossus activity increased briskly with further increases in chemical drive (1.1% ± 0.84%GG(MAX) per L/min increase in V(E)). In sleeping obstructive apnea patients: (1) Mechanoreceptor feedback is responsible for most of the genioglossus response to chemical drive. (2) Mechanoreceptor feedback is effective only above a threshold chemical drive, which varies greatly among patients. These findings account in part for the highly variable relation between pharyngeal mechanical abnormalities and apnea severity.

Potentiation of Chemical Ototoxicity by Noise

PubMed Central

Steyger, Peter S.

2010-01-01

High-intensity and/or prolonged exposure to noise causes temporary or permanent threshold shifts in auditory perception. Occupational exposure to solvents or administration of clinically important drugs, such as aminoglycoside antibiotics and cisplatin, also can induce permanent hearing loss. The mechanisms by which these ototoxic insults cause auditory dysfunction are still being unraveled, yet they share common sequelae, particularly generation of reactive oxygen species, that ultimately lead to hearing loss and deafness. Individuals are frequently exposed to ototoxic chemical contaminants (e.g., fuel) and noise simultaneously in a variety of work and recreational environments. Does simultaneous exposure to chemical ototoxins and noise potentiate auditory dysfunction? Exposure to solvent vapor in noisy environments potentiates the permanent threshold shifts induced by noise alone. Moderate noise levels potentiate both aminoglycoside- and cisplatin-induced ototoxicity in both rate of onset and in severity of auditory dysfunction. Thus, simultaneous exposure to chemical ototoxins and moderate levels of noise can potentiate auditory dysfunction. Preventing the ototoxic synergy of noise and chemical ototoxins requires removing exposure to ototoxins and/or attenuating noise exposure levels when chemical ototoxins are present. PMID:20523755

10 CFR 963.17 - Postclosure suitability criteria.

Code of Federal Regulations, 2014 CFR

2014-01-01

...) Near field geochemical environment—for example, the chemical reactions and products resulting from... probability and potential consequences of a self-sustaining nuclear reaction as a result of chemical or..., drip shields, backfill, coatings, or chemical modifications, and (ii) Waste package degradation—for...

10 CFR 963.17 - Postclosure suitability criteria.

Code of Federal Regulations, 2012 CFR

2012-01-01

...) Near field geochemical environment—for example, the chemical reactions and products resulting from... probability and potential consequences of a self-sustaining nuclear reaction as a result of chemical or..., drip shields, backfill, coatings, or chemical modifications, and (ii) Waste package degradation—for...

10 CFR 963.17 - Postclosure suitability criteria.

Code of Federal Regulations, 2010 CFR

2010-01-01

...) Near field geochemical environment—for example, the chemical reactions and products resulting from... probability and potential consequences of a self-sustaining nuclear reaction as a result of chemical or..., drip shields, backfill, coatings, or chemical modifications, and (ii) Waste package degradation—for...

10 CFR 963.17 - Postclosure suitability criteria.

Code of Federal Regulations, 2013 CFR

2013-01-01

...) Near field geochemical environment—for example, the chemical reactions and products resulting from... probability and potential consequences of a self-sustaining nuclear reaction as a result of chemical or..., drip shields, backfill, coatings, or chemical modifications, and (ii) Waste package degradation—for...

10 CFR 963.17 - Postclosure suitability criteria.

Code of Federal Regulations, 2011 CFR

2011-01-01

...) Near field geochemical environment—for example, the chemical reactions and products resulting from... probability and potential consequences of a self-sustaining nuclear reaction as a result of chemical or..., drip shields, backfill, coatings, or chemical modifications, and (ii) Waste package degradation—for...

Submilliampere continuous-wave room-temperature lasing operation of a GaAs mushroom structure surface-emitting laser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Y.J.; Dziura, T.G.; Wang, S.C.

1990-05-07

We report a GaAs mushroom structure surface-emitting laser at 900 nm with submilliampere (0.2--0.5 mA) threshold under room-temperature cw operation for the first time. The very low threshold current was achieved on devices which consisted of a 2--4 {mu}m diameter active region formed by chemical selective etching, and sandwiched between two Al{sub 0.05}Ga{sub 0.95} As/ Al{sub 0.53}Ga{sub 0.47} As distributed Bragg reflectors of very high reflectivity (98--99%) grown by metalorganic chemical vapor deposition.

Submilliampere continuous-wave room-temperature lasing operation of a GaAs mushroom structure surface-emitting laser

NASA Astrophysics Data System (ADS)

Yang, Ying Jay; Dziura, Thaddeus G.; Wang, S. C.; Hsin, Wei; Wang, Shyh

1990-05-01

We report a GaAs mushroom structure surface-emitting laser at 900 nm with submilliampere (0.2-0.5 mA) threshold under room-temperature cw operation for the first time. The very low threshold current was achieved on devices which consisted of a 2-4 μm diameter active region formed by chemical selective etching, and sandwiched between two Al0.05Ga0.95 As/ Al0.53Ga0.47 As distributed Bragg reflectors of very high reflectivity (98-99%) grown by metalorganic chemical vapor deposition.

Towards Enhanced Performance Thin-film Composite Membranes via Surface Plasma Modification

PubMed Central

Reis, Rackel; Dumée, Ludovic F.; Tardy, Blaise L.; Dagastine, Raymond; Orbell, John D.; Schutz, Jürg A.; Duke, Mikel C.

2016-01-01

Advancing the design of thin-film composite membrane surfaces is one of the most promising pathways to deal with treating varying water qualities and increase their long-term stability and permeability. Although plasma technologies have been explored for surface modification of bulk micro and ultrafiltration membrane materials, the modification of thin film composite membranes is yet to be systematically investigated. Here, the performance of commercial thin-film composite desalination membranes has been significantly enhanced by rapid and facile, low pressure, argon plasma activation. Pressure driven water desalination tests showed that at low power density, flux was improved by 22% without compromising salt rejection. Various plasma durations and excitation powers have been systematically evaluated to assess the impact of plasma glow reactions on the physico-chemical properties of these materials associated with permeability. With increasing power density, plasma treatment enhanced the hydrophilicity of the surfaces, where water contact angles decreasing by 70% were strongly correlated with increased negative charge and smooth uniform surface morphology. These results highlight a versatile chemical modification technique for post-treatment of commercial membrane products that provides uniform morphology and chemically altered surface properties. PMID:27363670

Mitigating Toxic Planktonic Cyanobacterial Blooms in Aquatic Ecosystems Facing Increasing Anthropogenic and Climatic Pressures

PubMed Central

2018-01-01

Toxic planktonic cyanobacterial blooms are a pressing environmental and human health problem. Blooms are expanding globally and threatening sustainability of our aquatic resources. Anthropogenic nutrient enrichment and hydrological modifications, including water diversions and reservoir construction, are major drivers of bloom expansion. Climatic change, i.e., warming, more extreme rainfall events, and droughts, act synergistically with human drivers to exacerbate the problem. Bloom mitigation steps, which are the focus of this review, must consider these dynamic interactive factors in order to be successful in the short- and long-term. Furthermore, these steps must be applicable along the freshwater to marine continuum connecting streams, lakes, rivers, estuarine, and coastal waters. There is an array of physical, chemical, and biological approaches, including flushing, mixing, dredging, application of algaecides, precipitating phosphorus, and selective grazing, that may arrest and reduce bloom intensities in the short-term. However, to ensure long term, sustainable success, targeting reductions of both nitrogen and phosphorus inputs should accompany these approaches along the continuum. Lastly, these strategies should accommodate climatic variability and change, which will likely modulate and alter nutrient-bloom thresholds. PMID:29419777

Delivery of high energy Er:YAG pulsed laser light at 2.94 µm through a silica hollow core photonic crystal fibre.

PubMed

Urich, A; Maier, R R J; Mangan, B J; Renshaw, S; Knight, J C; Hand, D P; Shephard, J D

2012-03-12

In this paper the delivery of high power Er:YAG laser pulses through a silica hollow core photonic crystal fibre is demonstrated. The Er:YAG wavelength of 2.94 µm is well beyond the normal transmittance of bulk silica but the unique hollow core guidance allows silica to guide in this regime. We have demonstrated for the first time the ability to deliver high energy pulses through an all-silica fibre at 2.94 µm. These silica fibres are mechanically and chemically robust, biocompatible and have low sensitivity to bending. A maximum pulse energy of 14 mJ at 2.94 µm was delivered through the fibre. This, to our knowledge, is the first time a silica hollow core photonic crystal fibre has been shown to transmit 2.94 μm laser light at a fluence exceeding the thresholds required for modification (e.g. cutting and drilling) of hard biological tissue. Consequently, laser delivery systems based on these fibres have the potential for the realization of novel, minimally-invasive surgical procedures.

Dependence of the optical conductivity on the uniaxial and biaxial strains in black phosphorene

NASA Astrophysics Data System (ADS)

Yang, C. H.; Zhang, J. Y.; Wang, G. X.; Zhang, C.

2018-06-01

By using the Kubo formula, the optical conductivity of strained black phosphorene was studied. The anisotropic band dispersion gives rise to an orientation dependent optical conductivity. The energy gap can be tuned by the uniaxial and biaxial strains which can be observed from the interband optical conductivity polarized along the armchair (x ) direction. The preferential conducting direction is along the x direction. The dependence of the intraband optical conductivity along the zigzag (y ) direction on the Fermi energy and strain exhibits increasing or decreasing monotonously. However, along the x direction this dependence is complicated which originates from the carriers' inverse-direction movements obtained by two types of the nearest phosphorus atom interactions. The modification of the biaxial strain on the energy structure and optical-absorption property is more effective. The imaginary part of the total optical conductivity (Im σ ) can be negative around the threshold of the interband optical transition by modifying the chemical potential. Away from this frequency region, Im σ exhibits positive value. It can be used in the application of the surface plasmon propagations in multilayer dielectric structures.

The influence of chemical methods (acid modification) on elephant foot yam flour to improve physical and chemical quality on processed food

NASA Astrophysics Data System (ADS)

Paramita, Octavianti; Wahyuningsih, Ansori, Muhammad

2018-03-01

This study was aimed at improving the physicochemical quality of elephant foot yam flour in Gunungpati, Semarang by acid modification. The utilization of elephant foot yam flour in several processed food was also discussed in this study. The flour of the experimental result discussed in this study was expected to become a reference for the manufacturers of elephant foot yam flour and its processed food in Gunungpati. This study modified the elephant foot yam flour using acid modification method. The physical and chemical quality of each elephant foot yam flour of the experimental result sample were assessed using proximate analysis. The resulting tuber flour weighed 50 grams and the soaked in acid solution with various concentrations 5 %, 10 % and 15 % with soaking duration 30, 60 and 90 minutes at temperature 35 °C. The resulting suspension was washed 3 times, filtered and then dried by cabinet dryer using 46 °C for 2 days. The dried flour was sifted with a 80 mesh sieve. Chemical test was conducted after elephant foot yam was acid modification to determine changes in the quality flour: test levels of protein, fat, crude fiber content, moisture content, ash content and starch content. In addition, color tests and granular test on elephant foot yam flour were also conducted. The acid modification as chemical treatment on elephant foot yam flour in this study was able to change the functional properties of elephant foot yam flour towards a better processing characterized by a brighter color (L = 80, a = 8 and b = 12), the hydrolysis of polysaccharides flour into shorter chain (flour content decreased to 72%), the expansion of granules in elephant foot yam resulting in a process - ready flour, and better monolayer water content of 11%. The content of protein and fiber on the elephant foot yam flour also can be maintained at a level of 8% and 1.9% levels.

40 CFR 49.153 - Applicability.

Code of Federal Regulations, 2014 CFR

2014-07-01

... negative value. If an emissions unit's post-change allowable emissions would be less than its pre-change... that program based on the actual-to-projected-actual test, it is considered a minor modification and is...-actual test is equal to or exceeds the minor NSR threshold listed in Table 1 of this section. For a...

Varying the optical properties of cholesteric liquid crystals

NASA Astrophysics Data System (ADS)

Relaix, Sabrina; Moreira, Michele; Palffy-Muhoray, Peter; Mitov, Michel

2008-03-01

Cholesteric Liquid Crystals (CLCs) are of particular interest as they form self-assembled photonic band gap (PBG) structures - a macroscopic helical structure, leading to a selective reflection of light - which can be easily tuned by external fields. As PBG materials, CLCs have been used as mirrorless lasers with low lasing thresholds since the density of photon states is suppressed in the reflection band and is enhanced at its edges [1]. The modification of the cholesteric organization -- either by the introduction of a pitch gradient across the cell or by the incorporation of nanoparticles in the medium -- has direct consequences on the PBG and hence the reflected intensity [2,3]. In this presentation, I will describe the variations in the optical properties of CLC caused by these modifications and will discuss possible applications, such as tuning the CLC laser wavelength or adjusting the laser threshold. [1] P. Palffy-Muhoray et al., Phil Trans R Soc A 364, 2747 (2006) [2] S. Relaix et al., Appl. Phys. Lett. 89, 251907 (2006) [3] S. Relaix et al., Liq. Cryst. 34, 1009 (2007)

Results of clinical olfactometric studies.

PubMed

Kittel, G

1976-09-01

A modification of a flow olfactometer with a new application appartus, with which "quasi-free" nasal respiration allows the elimination of adaptation without a special testing room, subsequent results using this device to examine olfactory thresholds before and after septum operations, as well as reference to threshold increases in 57 post-operative cases of cheilognathopalatoschisis are reported. An esthesio-neuroblastoma as well as the deformity syndrome with cheilognathopalatoschisis and encephalodystrophy are used as examples for combined olfactory transmission and perception disorders. Studies of 55 smokers with primary neurosensory disorders demonstrated a threefold increase in the olfactory threshold and an up to 50% decrease "fatique-time". A mean acetone deviation factor of 1.93 was seen in 100 students from 20-27 years of age before and after eating. Correspondingly, after a substantial breakfast and lunch, the olfactory threshold attained its maximum daily value within 90 minutes, much more pronounced than after intake of 80 grams of glucose solution. In contrast to the literature, the olfactory threshold was seen to continuously increase, dependent on age. Studies of the perceptive and recognition threshold on 100 normal individuals and 28 patients with hyposmia exhibited with 3 sigma, a significant difference. In patients with hyposmia, the absolute values for the two threshold types vary greatly, however not their deviation factors. More importance should be attached to the sense of smell as the so-called lesser senses give us the greatest pleasures.

Chemical Emergency Preparedness and Prevention Advisory: Swimming Pool Chemicals: Chlorine

EPA Pesticide Factsheets

This June 1990 advisory to Local Emergency Planning Committees (LEPCs) suggests they address risk from chlorine, an extremely hazardous substance, even when below the threshold planning quantity stated in Emergency Planning and Community Right-to-Know Act.

High-Throughput Pharmacokinetics for Environmental Chemicals (SOT)

EPA Science Inventory

High throughput screening (HTS) promises to allow prioritization of thousands of environmental chemicals with little or no in vivo information. For bioactivity identified by HTS, toxicokinetic (TK) models are essential to predict exposure thresholds below which no significant bio...

Development of Short-term Molecular Thresholds to Predict Long-term Mouse Liver Tumor Outcomes: Phthalate Case StudyTo be

EPA Science Inventory

Molecular Thresholds for Early Key Events in Liver Tumorgensis: PhthalateCase StudyTriangleShort-term changes in molecular profiles are a central component of strategies to model health effects of environmental chemicals such as phthalates, for which there is widespread human exp...

[Study on surface modification and biocompatibility of NiTi alloy intravascular stents].

PubMed

Shen, Yang; Wang, Gui-xue; Quan, Xue-jun; Yu, Qing-song

2006-01-01

This paper introduces the surface modification of NiTi alloy intravascular stents for roughness by chemical erosion and plasma deposition technology. The stent which had been granulated with chemical erosion was treated with TiO2 film prepared with Gel-sol. The study on the biocompatibility of the modified stent by the above two ways shows that the modified stent is rougher, and its anticoagulation and hydrophilicity are improved. However, the capability of erosion resistance is not enhanced significantly.

21 CFR 1313.53 - Waiver of modification of rules.

Code of Federal Regulations, 2010 CFR

2010-04-01

... EXPORTATION OF LIST I AND LIST II CHEMICALS Hearings § 1313.53 Waiver of modification of rules. The... in this part by notice in advance of the hearing, if he determines that no party in the hearing will...

Ultrafast Passive Shields for Laser and Ballistic Protection

DTIC Science & Technology

1991-07-15

chemically polymerized P(DPA)) as a binder, and these were tested for ablation (i.e. laser damage threshold ) limits. Table IV below summarizes these results...50, 100, 250 and 500 AJ/pulse o 1.G, 2.5, 5.0 mJ/pulse. The following energies were used for the preliminary laser damage threshold tests: o 2.5, 5.0...these were tested for ablation (i.e. laser damage threshold ) limits. Table VI summarizes these results which are all for tests in the absence of an iris

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kafka, Kyle R. P.; Hoffman, Brittany N.; Papernov, Semyon

The laser-induced damage threshold of fused-silica samples processed via magnetorheological finishing is investigated for polishing compounds depending on the type of abrasive material and the post-polishing surface roughness. The effectiveness of laser conditioning is examined using a ramped pre-exposure with the same 351-nm, 3-ns Gaussian pulses. Lastly, we examine chemical etching of the surface and correlate the resulting damage threshold to the etching protocol. A combination of etching and laser conditioning is found to improve the damage threshold by a factor of ~3, while maintaining <1-nm surface roughness.

40 CFR 60.489a - List of chemicals produced by affected facilities.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 7 2014-07-01 2014-07-01 false List of chemicals produced by affected... Equipment Leaks of VOC in the Synthetic Organic Chemicals Manufacturing Industry for Which Construction, Reconstruction, or Modification Commenced After November 7, 2006 § 60.489a List of chemicals produced by affected...

Chemical treatment of the intra-canal dentin surface: a new approach to modify dentin hydrophobicity

PubMed Central

GAITAN-FONSECA, Cesar; COLLART-DUTILLEUL, Pierre-Yves; SEMETEY, Vincent; ROMIEU, Olivier; CRUZ, Roel; FLORES, Hector; CUISINIER, Frédéric; PÉREZ, Elías; POZOS-GUILLEN, Amaury

2013-01-01

Objective: This study evaluated the hydrophobicity of dentin surfaces that were modified through chemical silanization with octadecyltrichlorosilane (OTS). Material and Methods: An in vitro experimental study was performed using 40 human permanent incisors that were divided into the following two groups: non-silanized and silanized. The specimens were pretreated and chemically modified with OTS. After the chemical modification, the dentin hydrophobicity was examined using a water contact angle measurement (WCA). The effectiveness of the modification of hydrophobicity was verified by the fluid permeability test (FPT). Results and Conclusions: Statistically significant differences were found in the values of WCA and FPT between the two groups. After silanization, the hydrophobic intraradicular dentin surface exhibited in vitro properties that limit fluid penetration into the sealed root canal. This chemical treatment is a new approach for improving the sealing of the root canal system. PMID:23559114

High Throughput Pharmacokinetics for Environmental Chemicals (FutureToxII)

EPA Science Inventory

Pharmacokinetic (PK) models are critical to determine whether chemical exposures produce potentially hazardous tissue concentrations. For bioactivity identified in vitro (e.g. ToxCast) – hazardous or not – PK models can forecast exposure thresholds, below which no significant bio...

40 CFR 370.12 - What hazardous chemicals must I report under this part?

Code of Federal Regulations, 2011 CFR

2011-07-01

... under OSHA HCS that is present at your facility equal to or above the applicable threshold specified in... required to have an MSDS and meets the definition of hazardous chemical under the OSHA regulations found at...

40 CFR 370.12 - What hazardous chemicals must I report under this part?

Code of Federal Regulations, 2010 CFR

2010-07-01

... under OSHA HCS that is present at your facility equal to or above the applicable threshold specified in... required to have an MSDS and meets the definition of hazardous chemical under the OSHA regulations found at...

40 CFR 455.47 - Pretreatment standards for new sources (PSNS).

Code of Federal Regulations, 2011 CFR

2011-07-01

...) EFFLUENT GUIDELINES AND STANDARDS PESTICIDE CHEMICALS Pesticide Chemicals Formulating and Packaging... Best Engineering Judgement for modifications not listed in Table 8 to this part 455); (2) The...

40 CFR 455.47 - Pretreatment standards for new sources (PSNS).

Code of Federal Regulations, 2010 CFR

2010-07-01

...) EFFLUENT GUIDELINES AND STANDARDS PESTICIDE CHEMICALS Pesticide Chemicals Formulating and Packaging... Best Engineering Judgement for modifications not listed in Table 8 to this part 455); (2) The...

15 CFR Supplement No. 2 to Part 714 - Deadlines for Submission of Schedule 3 Declarations, Reports, and Amendments

Code of Federal Regulations, 2010 CFR

2010-01-01

... Relating to Commerce and Foreign Trade (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS Pt. 714, Supp. 2... Schedule 3 chemical exceeded the declaration threshold in § 714.1(a)(1)(i) of the CWCR. Annual Report on...

21 CFR 1313.22 - Contents of export declaration.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 9 2010-04-01 2010-04-01 false Contents of export declaration. 1313.22 Section... EXPORTATION OF LIST I AND LIST II CHEMICALS Exportation of Listed Chemicals § 1313.22 Contents of export... quantitative threshold criteria established in § 1310.04(f) of this chapter may be exported if that chemical is...

Polydopamine-mediated surface modification of scaffold materials for human neural stem cell engineering.

PubMed

Yang, Kisuk; Lee, Jung Seung; Kim, Jin; Lee, Yu Bin; Shin, Heungsoo; Um, Soong Ho; Kim, Jeong Beom; Park, Kook In; Lee, Haeshin; Cho, Seung-Woo

2012-10-01

Surface modification of tissue engineering scaffolds and substrates is required for improving the efficacy of stem cell therapy by generating physicochemical stimulation promoting proliferation and differentiation of stem cells. However, typical surface modification methods including chemical conjugation or physical absorption have several limitations such as multistep, complicated procedures, surface denaturation, batch-to-batch inconsistencies, and low surface conjugation efficiency. In this study, we report a mussel-inspired, biomimetic approach to surface modification for efficient and reliable manipulation of human neural stem cell (NSC) differentiation and proliferation. Our study demonstrates that polydopamine coating facilitates highly efficient, simple immobilization of neurotrophic growth factors and adhesion peptides onto polymer substrates. The growth factor or peptide-immobilized substrates greatly enhance differentiation and proliferation of human NSCs (human fetal brain-derived NSCs and human induced pluripotent stem cell-derived NSCs) at a level comparable or greater than currently available animal-derived coating materials (Matrigel) with safety issues. Therefore, polydopamine-mediated surface modification can provide a versatile platform technology for developing chemically defined, safe, functional substrates and scaffolds for therapeutic applications of human NSCs. Copyright © 2012 Elsevier Ltd. All rights reserved.

Comparison of some effects of modification of a polylactide surface layer by chemical, plasma, and laser methods

NASA Astrophysics Data System (ADS)

Moraczewski, Krzysztof; Rytlewski, Piotr; Malinowski, Rafał; Żenkiewicz, Marian

2015-08-01

The article presents the results of studies and comparison of selected properties of the modified PLA surface layer. The modification was carried out with three methods. In the chemical method, a 0.25 M solution of sodium hydroxide in water and ethanol was utilized. In the plasma method, a 50 W generator was used, which produced plasma in the air atmosphere under reduced pressure. In the laser method, a pulsed ArF excimer laser with fluency of 60 mJ/cm2 was applied. Polylactide samples were examined by using the following techniques: scanning electron microscopy (SEM), atomic force microscopy (AFM), goniometry and X-ray photoelectron spectroscopy (XPS). Images of surfaces of the modified samples were recorded, contact angles were measured, and surface free energy was calculated. Qualitative and quantitative analyses of chemical composition of the PLA surface layer were performed as well. Based on the survey it was found that the best modification results are obtained using the plasma method.

Expanding the Bioactive Chemical Space of Anthrabenzoxocinones through Engineering the Highly Promiscuous Biosynthetic Modification Steps.

PubMed

Mei, Xianyi; Yan, Xiaoli; Zhang, Hui; Yu, Mingjia; Shen, Guangqing; Zhou, Linjun; Deng, Zixin; Lei, Chun; Qu, Xudong

2018-01-19

Anthrabenzoxocinones (ABXs) including (-)-ABXs and (+)-ABXs are a group of bacterial FabF-specific inhibitors with potent antimicrobial activity of resistant strains. Optimization of their chemical structures is a promising method to develop potent antibiotics. Through biosynthetic investigation, we herein identified and characterized two highly promiscuous enzymes involved in the (-)-ABX structural modification. The promiscuous halogenase and methyltransferase can respectively introduce halogen-modifications into various positions of the ABX scaffolds and methylation to highly diverse substrates. Manipulation of their activity in both of the (-)-ABXs and (+)-ABXs biosyntheses led to the generation of 14 novel ABX analogues of both enantiomers. Bioactivity assessment revealed that a few of the analogues showed significantly improved antimicrobial activity, with the C3-hydroxyl and chlorine substitutions critical for their activity. This study enormously expands the bioactive chemical space of the ABX family and FabF-specific inhibitors. The disclosed broad-selective biosynthetic machineries and structure-activity relationship provide a solid basis for further generation of potent antimicrobial agents.

Control of peptide nanotube diameter by chemical modifications of an aromatic residue involved in a single close contact

PubMed Central

Tarabout, Christophe; Roux, Stéphane; Gobeaux, Frédéric; Fay, Nicolas; Pouget, Emilie; Meriadec, Cristelle; Ligeti, Melinda; Thomas, Daniel; IJsselstijn, Maarten; Besselievre, François; Buisson, David-Alexandre; Verbavatz, Jean-Marc; Petitjean, Michel; Valéry, Céline; Perrin, Lionel; Rousseau, Bernard; Artzner, Franck; Paternostre, Maité; Cintrat, Jean-Christophe

2011-01-01

Supramolecular self-assembly is an attractive pathway for bottom-up synthesis of novel nanomaterials. In particular, this approach allows the spontaneous formation of structures of well-defined shapes and monodisperse characteristic sizes. Because nanotechnology mainly relies on size-dependent physical phenomena, the control of monodispersity is required, but the possibility of tuning the size is also essential. For self-assembling systems, shape, size, and monodispersity are mainly settled by the chemical structure of the building block. Attempts to change the size notably by chemical modification usually end up with the loss of self-assembly. Here, we generated a library of 17 peptides forming nanotubes of monodisperse diameter ranging from 10 to 36 nm. A structural model taking into account close contacts explains how a modification of a few Å of a single aromatic residue induces a fourfold increase in nanotube diameter. The application of such a strategy is demonstrated by the formation of silica nanotubes of various diameters. PMID:21518895

Chemical modification of uniform soils and soils with high/low plasticity index.

DOT National Transportation Integrated Search

2016-08-01

The addition of chemicals into the subgrade has been widely used during construction to improve the soil properties. The chemicals, often Lime Kiln Dust (LKD) and Portland cement, are added to the soil to improve its workability, compactability and e...

Evaluating Pharmacokinetic and Pharmacodynamic Interactions with Computational Models in Cumulative Risk Assessment

EPA Science Inventory

Simultaneous or sequential exposure to multiple chemicals may cause interactions in the pharmacokinetics (PK) and/or pharmacodynamics (PD) of the individual chemicals. Such interactions can cause modification of the internal or target dose/response of one chemical in the mixture ...

Biological response to purification and acid functionalization of carbon nanotubes

NASA Astrophysics Data System (ADS)

Figarol, Agathe; Pourchez, Jérémie; Boudard, Delphine; Forest, Valérie; Tulliani, Jean-Marc; Lecompte, Jean-Pierre; Cottier, Michèle; Bernache-Assollant, Didier; Grosseau, Philippe

2014-07-01

Acid functionalization has been considered as an easy way to enhance the dispersion and biodegradation of carbon nanotubes (CNT). However, inconsistencies between toxicity studies of acid functionalized CNT remain unexplained. This could be due to a joint effect of the main physicochemical modifications resulting from an acid functionalization: addition of surface acid groups and purification from catalytic metallic impurities. In this study, the impact on CNT biotoxicity of these two physiochemical features was assessed separately. The in vitro biological response of RAW 264.7 macrophages was evaluated after exposure to 15-240 µg mL-1 of two types of multi-walled CNT. For each type of CNT (small: 20 nm diameter, and big: 90 nm diameter), three different surface chemical properties were studied (total of six CNT samples): pristine, acid functionalized and desorbed. Desorbed CNT were purified by the acid functionalization but presented a very low amount of surface acid groups due to a thermal treatment under vacuum. A Janus effect of acid functionalization with two opposite impacts is highlighted. The CNT purification decreased the overall toxicity, while the surface acid groups intensified it when present at a specific threshold. These acid groups especially amplified the pro-inflammatory response. The threshold mechanism which seemed to regulate the impact of acid groups should be further studied to determine its value and potential link to the other physicochemical state of the CNT. The results suggest that, for a safer-design approach, the benefit-risk balance of an acid functionalization has to be considered, depending on the CNT primary state of purification. Further research should be conducted in this direction.

40 CFR 455.46 - Pretreatment standards for existing sources (PSES).

Code of Federal Regulations, 2014 CFR

2014-07-01

...) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) PESTICIDE CHEMICALS Pesticide Chemicals Formulating and... listed in Table 8 to this part 455 (or received a modification by Best Engineering Judgement for...

40 CFR 455.46 - Pretreatment standards for existing sources (PSES).

Code of Federal Regulations, 2011 CFR

2011-07-01

...) EFFLUENT GUIDELINES AND STANDARDS PESTICIDE CHEMICALS Pesticide Chemicals Formulating and Packaging... listed in Table 8 to this part 455 (or received a modification by Best Engineering Judgement for...

40 CFR 455.46 - Pretreatment standards for existing sources (PSES).

Code of Federal Regulations, 2012 CFR

2012-07-01

...) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) PESTICIDE CHEMICALS Pesticide Chemicals Formulating and... listed in Table 8 to this part 455 (or received a modification by Best Engineering Judgement for...

40 CFR 455.46 - Pretreatment standards for existing sources (PSES).

Code of Federal Regulations, 2010 CFR

2010-07-01

...) EFFLUENT GUIDELINES AND STANDARDS PESTICIDE CHEMICALS Pesticide Chemicals Formulating and Packaging... listed in Table 8 to this part 455 (or received a modification by Best Engineering Judgement for...

Evaluating the environmental hazard of industrial chemicals from data collected during the REACH registration process.

PubMed

Gustavsson, Mikael B; Hellohf, Andreas; Backhaus, Thomas

2017-05-15

Registration dossiers for 11,678 industrial chemicals were retrieved from the database of the European Chemicals Agency, of which 3566 provided a numerical entry for the corresponding predicted no effect concentration for the freshwater environment (PNEC). A distribution-based examination of 2244 of these entries reveals that the average PNEC of an industrial chemical in Europe is 238nmol/L, covering a span of 9 orders of magnitude. A comparison with biocides, pesticides, pharmaceuticals and WFD-priority pollutants reveals that, in average, industrial chemicals are least hazardous (hazard ranking: industrial chemicals≪pharmaceuticals

The Influence of Chemical Modification on Linker Rotational Dynamics in Metal-Organic Frameworks.

PubMed

Damron, Joshua T; Ma, Jialiu; Kurz, Ricardo; Saalwächter, Kay; Matzger, Adam J; Ramamoorthy, Ayyalusamy

2018-05-21

The robust synthetic flexibility of metal-organic frameworks (MOFs) offers a promising class of tailorable materials, for which the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid-state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated-local-field NMR approach to show how specific intraframework chemical modifications to MOF UiO-66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A quantitative strategy to detect changes in accessibility of protein regions to chemical modification on heterodimerization

PubMed Central

Dreger, Mathias; Leung, Bo Wah; Brownlee, George G; Deng, Tao

2009-01-01

We describe a method for studying quantitative changes in accessibility of surface lysine residues of the PB1 subunit of the influenza RNA polymerase as a result of association with the PA subunit to form a PB1-PA heterodimer. Our method combines two established methods: (i) the chemical modification of surface lysine residues of native proteins by N-hydroxysuccinimidobiotin (NHS-biotin) and (ii) the stable isotope labeling of amino acids in cell culture (SILAC) followed by tryptic digestion and mass spectrometry. By linking the chemical modification with the SILAC methodology for the first time, we obtain quantitative data on chemical modification allowing subtle changes in accessibility to be described. Five regions in the PB1 monomer showed altered reactivity to NHS-biotin when compared with the [PB1-PA] heterodimer. Mutational analysis of residues in two such regions—at K265 and K481 of PB1, which were about three- and twofold, respectively, less accessible to biotinylation in the PB1-PA heterodimer compared with the PB1 monomer, demonstrated that both K265 and K481 were crucial for polymerase function. This novel assay of quantitative profiling of biotinylation patterns (Q-POP assay) highlights likely conformational changes at important functional sites, as observed here for PB1, and may provide information on protein–protein interaction interfaces. The Q-POP assay should be a generally applicable approach and may detect novel functional sites suitable for targeting by drugs. PMID:19517532

Apparatus and methods for detecting chemical permeation

DOEpatents

Vo-Dinh, Tuan

1994-01-01

Apparatus and methods for detecting the permeation of hazardous or toxic chemicals through protective clothing are disclosed. The hazardous or toxic chemicals of interest do not possess the spectral characteristic of luminescence. The apparatus and methods utilize a spectrochemical modification technique to detect the luminescence quenching of an indicator compound which upon permeation of the chemical through the protective clothing, the indicator is exposed to the chemical, thus indicating chemical permeation.

Chemical and Conformational Diversity of Modified Nucleosides Affects tRNA Structure and Function.

PubMed

Väre, Ville Y P; Eruysal, Emily R; Narendran, Amithi; Sarachan, Kathryn L; Agris, Paul F

2017-03-16

RNAs are central to all gene expression through the control of protein synthesis. Four major nucleosides, adenosine, guanosine, cytidine and uridine, compose RNAs and provide sequence variation, but are limited in contributions to structural variation as well as distinct chemical properties. The ability of RNAs to play multiple roles in cellular metabolism is made possible by extensive variation in length, conformational dynamics, and the over 100 post-transcriptional modifications. There are several reviews of the biochemical pathways leading to RNA modification, but the physicochemical nature of modified nucleosides and how they facilitate RNA function is of keen interest, particularly with regard to the contributions of modified nucleosides. Transfer RNAs (tRNAs) are the most extensively modified RNAs. The diversity of modifications provide versatility to the chemical and structural environments. The added chemistry, conformation and dynamics of modified nucleosides occurring at the termini of stems in tRNA's cloverleaf secondary structure affect the global three-dimensional conformation, produce unique recognition determinants for macromolecules to recognize tRNAs, and affect the accurate and efficient decoding ability of tRNAs. This review will discuss the impact of specific chemical moieties on the structure, stability, electrochemical properties, and function of tRNAs.

Surface Engineering of ITO Substrates to Improve the Memory Performance of an Asymmetric Conjugated Molecule with a Side Chain.

PubMed

Hou, Xiang; Cheng, Xue-Feng; Xiao, Xin; He, Jing-Hui; Xu, Qing-Feng; Li, Hua; Li, Na-Jun; Chen, Dong-Yun; Lu, Jian-Mei

2017-09-05

Organic multilevel random resistive access memory (RRAM) devices with an electrode/organic layer/electrode sandwich-like structure suffer from poor reproducibility, such as low effective ternary device yields and a wide threshold voltage distribution, and improvements through organic material renovation are rather limited. In contrast, engineering of the electrode surfaces rather than molecule design has been demonstrated to boost the performance of organic electronics effectively. Herein, we introduce surface engineering into organic multilevel RRAMs to enhance their ternary memory performance. A new asymmetric conjugated molecule composed of phenothiazine and malononitrile with a side chain (PTZ-PTZO-CN) was fabricated in an indium tin oxide (ITO)/PTZ-PTZO-CN/Al sandwich-like memory device. Modification of the ITO substrate with a phosphonic acid (PA) prior to device fabrication increased the ternary device yield (the ratio of effective ternary device) and narrowed the threshold voltage distribution. The crystallinity analysis revealed that PTZ-PTZO-CN grown on untreated ITO crystallized into two phases. After the surface engineering of ITO, this crystalline ambiguity was eliminated and a sole crystal phase was obtained that was the same as in the powder state. The unified crystal structure and improved grain mosaicity resulted in a lower threshold voltage and, therefore, a higher ternary device yield. Our result demonstrated that PA modification also improved the memory performance of an asymmetric conjugated molecule with a side chain. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Real-time in situ study of femtosecond-laser-induced periodic structures on metals by linear and nonlinear optics.

PubMed

Zhang, Jihua; He, Yizhuo; Lam, Billy; Guo, Chunlei

2017-08-21

Femtosecond-laser surface structuring on metals is investigated in real time by both fundamental and second harmonic generation (SHG) signals. The onset of surface modification and its progress can be monitored by both the fundamental and SHG probes. However, the dynamics of femtosecond-laser-induced periodic surface structures (FLIPSSs) formation can only be revealed by SHG but not fundamental because of the higher sensitivity of SHG to structural geometry on metal. Our technique provides a simple and effective way to monitor the surface modification and FLIPSS formation thresholds and allows us to obtain the optimal FLIPSS for SHG enhancement.

ASTM Data Banks and Chemical Information Sources

ERIC Educational Resources Information Center

Batik, Albert; Hale, Eleanor

1972-01-01

Among the data described are infrared indexes, mass spectral data, chromatographic data, X-ray emmission data, odor and taste threshold data, and thermodynamics data. This paper provides the chemical documentarian a complete reference source to a wide variety of analytical data. (Author/NH)

A revised framework for coupled human and natural systems, propagating thresholds, and managing environmental problems

NASA Astrophysics Data System (ADS)

Stevenson, R. Jan

Frameworks for solving environmental problems have been presented over the past 40 years from many organizations and disciplines, often with a strong focus on their own discipline. This paper describes a modification of an existing framework that can be better applied to manage environmental problems. Human well being, environmental policy, human activities, stressors (contaminants and habitat alterations), and ecosystem services are highlighted as five elements of the coupled human and natural system in the proposed framework. Thresholds in relationships among elements in coupled human and natural systems are key attributes of couplings because of their use in development of environmental criteria by facilitating stakeholder consensus and preventing catastrophic changes. Propagation of thresholds through coupled human and natural systems is hypothesized to be a significant driver of policy development. The application of the framework is related to managing eutrophication and algal bloom problems.

A longitudinal study on postoperative hearing thresholds with the Vibrant Soundbridge device.

PubMed

Vincent, C; Fraysse, B; Lavieille, J-P; Truy, E; Sterkers, O; Vaneecloo, F-M

2004-10-01

The Vibrant Soundbridge is a semi-implantable middle ear hearing device used in the rehabilitation of adults with sensorineural hearing loss. In order to evaluate the long-term effects of the implanted part of the device, audiological data from 39 patients implanted over several implant sites across France were collected and analyzed retrospectively. The mean follow-up time was 16 months; 25 patients had a follow-up period of over 1 year. Surgery was uneventful in all cases. The present study of the 39 implanted patients with a mid- to long-term follow-up found a statistically significant modification of hearing thresholds (pre- versus postoperative) for frequencies of 0.5 and 4 kHz. However, the shift of threshold was rather limited (2.79 and 3.34 dB, respectively), and this variation was not statistically different from the evolution of the opposite non-operated ear.

Accelerated Path-following Iterative Shrinkage Thresholding Algorithm with Application to Semiparametric Graph Estimation

PubMed Central

Zhao, Tuo; Liu, Han

2016-01-01

We propose an accelerated path-following iterative shrinkage thresholding algorithm (APISTA) for solving high dimensional sparse nonconvex learning problems. The main difference between APISTA and the path-following iterative shrinkage thresholding algorithm (PISTA) is that APISTA exploits an additional coordinate descent subroutine to boost the computational performance. Such a modification, though simple, has profound impact: APISTA not only enjoys the same theoretical guarantee as that of PISTA, i.e., APISTA attains a linear rate of convergence to a unique sparse local optimum with good statistical properties, but also significantly outperforms PISTA in empirical benchmarks. As an application, we apply APISTA to solve a family of nonconvex optimization problems motivated by estimating sparse semiparametric graphical models. APISTA allows us to obtain new statistical recovery results which do not exist in the existing literature. Thorough numerical results are provided to back up our theory. PMID:28133430

Could ecological thresholds of toxicological concern (eco-TTCs) be used to support development of ambient water quality criteria?

EPA Science Inventory

The Threshold of Toxicologic Concern (TTC) is an approach used for a decades in human hazard assessment. A TTC establishes an exposure level for a chemical below which no appreciable risk to human health is expected based upon a de minimis value for toxicity identified for many ...

Bio-Inspired Nanomaterials: Protein Cage Nano-Architectures

DTIC Science & Technology

2008-04-01

chemical modification of protein cage materials and controlled chemical synthesis under mild biological conditions. High- resolution structural...properties based on a combination of controlled mobility and metal ligand interactions. Using the exterior surface of the CCMV viral cage we have chemically ...follows: Patterning by microplotter was achieved by depositing a preselected antibody solution directly onto chemically activated silicon or gold

Biophysical analysis of the effect of chemical modification by 4-oxononenal on the structure, stability, and function of binding immunoglobulin protein (BiP)

PubMed Central

Shah, Dinen D.; Singh, Surinder M.; Dzieciatkowska, Monika

2017-01-01

Binding immunoglobulin protein (BiP) is a molecular chaperone important for the folding of numerous proteins, which include millions of immunoglobulins in human body. It also plays a key role in the unfolded protein response (UPR) in the endoplasmic reticulum. Free radical generation is a common phenomenon that occurs in cells under healthy as well as under stress conditions such as ageing, inflammation, alcohol consumption, and smoking. These free radicals attack the cell membranes and generate highly reactive lipid peroxidation products such as 4-oxononenal (4-ONE). BiP is a key protein that is modified by 4-ONE. In this study, we probed how such chemical modification affects the biophysical properties of BiP. Upon modification, BiP shows significant tertiary structural changes with no changes in its secondary structure. The protein loses its thermodynamic stability, particularly, that of the nucleotide binding domain (NBD) where ATP binds. In terms of function, the modified BiP completely loses its ATPase activity with decreased ATP binding affinity. However, modified BiP retains its immunoglobulin binding function and its chaperone activity of suppressing non-specific protein aggregation. These results indicate that 4-ONE modification can significantly affect the structure-function of key proteins such as BiP involved in cellular pathways, and provide a molecular basis for how chemical modifications can result in the failure of quality control mechanisms inside the cell. PMID:28886061

Causes of genome instability: the effect of low dose chemical exposures in modern society.

PubMed

Langie, Sabine A S; Koppen, Gudrun; Desaulniers, Daniel; Al-Mulla, Fahd; Al-Temaimi, Rabeah; Amedei, Amedeo; Azqueta, Amaya; Bisson, William H; Brown, Dustin G; Brunborg, Gunnar; Charles, Amelia K; Chen, Tao; Colacci, Annamaria; Darroudi, Firouz; Forte, Stefano; Gonzalez, Laetitia; Hamid, Roslida A; Knudsen, Lisbeth E; Leyns, Luc; Lopez de Cerain Salsamendi, Adela; Memeo, Lorenzo; Mondello, Chiara; Mothersill, Carmel; Olsen, Ann-Karin; Pavanello, Sofia; Raju, Jayadev; Rojas, Emilio; Roy, Rabindra; Ryan, Elizabeth P; Ostrosky-Wegman, Patricia; Salem, Hosni K; Scovassi, A Ivana; Singh, Neetu; Vaccari, Monica; Van Schooten, Frederik J; Valverde, Mahara; Woodrick, Jordan; Zhang, Luoping; van Larebeke, Nik; Kirsch-Volders, Micheline; Collins, Andrew R

2015-06-01

Genome instability is a prerequisite for the development of cancer. It occurs when genome maintenance systems fail to safeguard the genome's integrity, whether as a consequence of inherited defects or induced via exposure to environmental agents (chemicals, biological agents and radiation). Thus, genome instability can be defined as an enhanced tendency for the genome to acquire mutations; ranging from changes to the nucleotide sequence to chromosomal gain, rearrangements or loss. This review raises the hypothesis that in addition to known human carcinogens, exposure to low dose of other chemicals present in our modern society could contribute to carcinogenesis by indirectly affecting genome stability. The selected chemicals with their mechanisms of action proposed to indirectly contribute to genome instability are: heavy metals (DNA repair, epigenetic modification, DNA damage signaling, telomere length), acrylamide (DNA repair, chromosome segregation), bisphenol A (epigenetic modification, DNA damage signaling, mitochondrial function, chromosome segregation), benomyl (chromosome segregation), quinones (epigenetic modification) and nano-sized particles (epigenetic pathways, mitochondrial function, chromosome segregation, telomere length). The purpose of this review is to describe the crucial aspects of genome instability, to outline the ways in which environmental chemicals can affect this cancer hallmark and to identify candidate chemicals for further study. The overall aim is to make scientists aware of the increasing need to unravel the underlying mechanisms via which chemicals at low doses can induce genome instability and thus promote carcinogenesis. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Review of laboratory-based terrestrial bioaccumulation assessment approaches for organic chemicals: Current status and future possibilities.

PubMed

Hoke, Robert; Huggett, Duane; Brasfield, Sandra; Brown, Becky; Embry, Michelle; Fairbrother, Anne; Kivi, Michelle; Paumen, Miriam Leon; Prosser, Ryan; Salvito, Dan; Scroggins, Rick

2016-01-01

In the last decade, interest has been renewed in approaches for the assessment of the bioaccumulation potential of chemicals, principally driven by the need to evaluate large numbers of chemicals as part of new chemical legislation, while reducing vertebrate test organism use called for in animal welfare legislation. This renewed interest has inspired research activities and advances in bioaccumulation science for neutral organic chemicals in aquatic environments. In January 2013, ILSI Health and Environmental Sciences Institute convened experts to identify the state of the science and existing shortcomings in terrestrial bioaccumulation assessment of neutral organic chemicals. Potential modifications to existing laboratory methods were identified, including areas in which new laboratory approaches or test methods could be developed to address terrestrial bioaccumulation. The utility of "non-ecotoxicity" data (e.g., mammalian laboratory data) was also discussed. The highlights of the workshop discussions are presented along with potential modifications in laboratory approaches and new test guidelines that could be used for assessing the bioaccumulation of chemicals in terrestrial organisms. © 2015 SETAC.

Odor from a chemical perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wray, T.K.

1995-06-01

Early odor-detection measurements categorized chemicals according to odor quality. Recent methods focus on the odor threshold, or the quantitative amount of a chemical in air that can be detected by the human sense of smell. Researchers characterize and quantify odor using an array of sensory and analytical procedures. Humans possess one of the dullest mammalian senses of smell; however, they can recognize about 10,000 distinct odors at concentrations ranging from less than 1 part per billion to several hundred thousand parts per million. Each time humans inhale, they chemically analyze microscopic pieces of the environment that make physical contact withmore » the nerves in their noses. Individual molecules travel up the nose to a sheet of moist, mucus-bathed tissue that consists of about 5 million smell-sensing, olfactory neurons. After dissolving in the mucus, odor molecules ``float`` into appropriately shaped receptor pockets. A series of cellular reactions then transmit impulses to the limbic system, hippocampus and, finally, the neocortex. Odor detection is an important defense mechanism. The author presents the odor thresholds for selected organic compounds, and other hazardous chemicals.« less

Incorporation of unnatural sugars for the identification of glycoproteins.

PubMed

Zaro, Balyn W; Hang, Howard C; Pratt, Matthew R

2013-01-01

Glycosylation is an abundant post-translational modification that alters the fate and function of its substrate proteins. To aid in understanding the significance of protein glycosylation, identification of target proteins is key. As with all proteomics experiments, mass spectrometry has been established as the desired method for substrate identification. However, these approaches require selective enrichment and purification of modified proteins. Chemical reporters in combination with bioorthogonal reactions have emerged as robust tools for identifying post-translational modifications including glycosylation. We provide here a method for the use of bioorthogonal chemical reporters for isolation and identification of glycosylated proteins. More specifically, this protocol is a representative procedure from our own work using an alkyne-bearing O-GlcNAc chemical reporter (GlcNAlk) and a chemically cleavable azido-azo-biotin probe for the identification of O-GlcNAc-modified proteins.

Novel approach for classifying chemicals according to skin sensitizing potency by non-radioisotopic modification of the local lymph node assay.

PubMed

Takeyoshi, Masahiro; Iida, Kenji; Shiraishi, Keiji; Hoshuyama, Satsuki

2005-01-01

The murine local lymph node assay (LLNA) is currently recognized as a stand-alone sensitization test for determining the sensitizing potential of chemicals, and it has the advantage of yielding a quantitative endpoint that can be used to predict the sensitization potency of chemicals. The EC3 has been proposed as a parameter for classifying chemicals according to the sensitization potency. We previously developed a non-radioisotopic endpoint for the LLNA based on 5-bromo-2'-deoxyuridine (BrdU) incorporation (non-RI LLNA), and we are proposing a new procedure to predict the sensitization potency of chemicals based on comparisons with known human contact allergens. Nine chemicals (i.e. diphencyclopropenone, p-phenylenediamine, glutaraldehyde, cinnamicaldehyde, citral, eugenol, isopropyl myristate, propyleneglycol and hexane) categorized as human contact allergen classes 1-5 were tested by the non-RI LLNA with the following reference allergens: 2,4-dinitrochlorobenzene (DNCB) as a class 1 human contact allergen, isoeugenol as a class 2 human contact allergen and alpha-hexylcinnamic aldehyde (HCA) as a class 3 human contact allergen. Consequently, nine test chemicals were almost assigned to their correct allergen class. The results suggested that the new procedure for non-RI LLNA can provide correct sensitization potency data. Sensitization potency data are useful for evaluating the sensitization risk to humans of exposure to new chemical products. Accordingly, this approach would be an effective modification of LLNA with regard to its experimental design. Moreover, this procedure can be applied also to the standard LLNA with radioisotopes and to other modifications of the LLNA. Copyright 2005 John Wiley & Sons, Ltd.

Physical modification of palm kernel meal improved available carbohydrate, physicochemical properties and in vitro digestibility in economic freshwater fish.

PubMed

Thongprajukaew, Karun; Yawang, Pinya; Dudae, Lateepah; Bilanglod, Husna; Dumrongrittamatt, Terdtoon; Tantikitti, Chutima; Kovitvadhi, Uthaiwan

2013-12-01

Unavailable carbohydrates are an important limiting factor for utilization of palm kernel meal (PKM) as aquafeed ingredients. The aim of this study was to improve available carbohydrate from PKM. Different physical modifications including water soaking, microwave irradiation, gamma irradiation and electron beam, were investigated in relation to chemical composition, physicochemical properties and in vitro carbohydrate digestibility using digestive enzymes from economic freshwater fish. Modified methods had significant (P < 0.05) effects on chemical composition by decreasing crude fiber and increasing available carbohydrates. Improvements in physicochemical properties of PKM, such as water solubility, microstructure, relative crystallinity and lignocellulosic spectra, were mainly achieved by soaking and microwave irradiation. Carbohydrate digestibility varied among the physical modifications tested (P < 0.05) and three fish species had different abilities to digest PKM. Soaking was the appropriate modification for increasing carbohydrate digestion specifically in Nile tilapia (Oreochromis niloticus), whereas either soaking or microwave irradiation was effective for striped snakehead (Channa striata). For walking catfish (Clarias batrachus), carbohydrate digestibility was similar among raw, soaked and microwave-irradiated PKM. These findings suggest that soaking and microwave irradiation could be practical methods for altering appropriate physicochemical properties of PKM as well as increasing carbohydrate digestibility in select economic freshwater fish. © 2013 Society of Chemical Industry.

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.

Code of Federal Regulations, 2013 CFR

2013-01-01

... reports of exports and imports of Schedule 2 chemicals—(1) Declarations. A Schedule 2 plant site that is declared because it produced, processed or consumed a Schedule 2 chemical at one or more plants above the... plant site that same Schedule 2 chemical above the applicable threshold, must submit export and import...

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.

Code of Federal Regulations, 2014 CFR

2014-01-01

... reports of exports and imports of Schedule 2 chemicals—(1) Declarations. A Schedule 2 plant site that is declared because it produced, processed or consumed a Schedule 2 chemical at one or more plants above the... plant site that same Schedule 2 chemical above the applicable threshold, must submit export and import...

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.

Code of Federal Regulations, 2012 CFR

2012-01-01

... reports of exports and imports of Schedule 2 chemicals—(1) Declarations. A Schedule 2 plant site that is declared because it produced, processed or consumed a Schedule 2 chemical at one or more plants above the... plant site that same Schedule 2 chemical above the applicable threshold, must submit export and import...

Peripheral absolute threshold spectral sensitivity in retinitis pigmentosa.

PubMed Central

Massof, R W; Johnson, M A; Finkelstein, D

1981-01-01

Dark-adapted spectral sensitivities were measured in the peripheral retinas of 38 patients diagnosed as having typical retinitis pigmentosa (RP) and in 3 normal volunteers. The patients included those having autosomal dominant and autosomal recessive inheritance patterns. Results were analysed by comparisons with the CIE standard scotopic spectral visibility function and with Judd's modification of the photopic spectral visibility function, with consideration of contributions from changes in spectral transmission of preretinal media. The data show 3 general patterns. One group of patients had absolute threshold spectral sensitivities that were fit by Judd's photopic visibility curve. Absolute threshold spectral sensitivities for a second group of patients were fit by a normal scotopic spectral visibility curve. The third group of patients had absolute threshold spectral sensitivities that were fit by a combination of scotopic and photopic spectral visibility curves. The autosomal dominant and autosomal recessive modes of inheritance were represented in each group of patients. These data indicate that RP patients have normal rod and/or cone spectral sensitivities, and support the subclassification of patients described previously by Massof and Finkelstein. PMID:7459312

Estimation of ultrashort laser irradiation effect over thin transparent biopolymer films morphology

NASA Astrophysics Data System (ADS)

Daskalova, A.; Nathala, C.; Bliznakova, I.; Slavov, D.; Husinsky, W.

2015-01-01

The collagen - elastin biopolymer thin films treated by CPA Ti:Sapphire laser (Femtopower - Compact Pro) at 800nm central wavelength with 30fs and 1kHz repetition rate are investigated. A process of surface modifications and microporous scaffold creation after ultrashort laser irradiation has been observed. The single-shot (N=1) and multi-shot (N<1) ablation threshold values were estimated by studying the linear relationship between the square of the crater diameter D2 and the logarithm of the laser fluence F for determination of the threshold fluences for N=1, 2, 5, 10, 15 and 30 number of laser pulses. The incubation analysis by calculation of the incubation coefficient ξ for multi - shot fluence threshold for selected materials by power - law relationship form Fth(N)=Fth(1)Nξ-1 was also obtained. In this paper, we have also shown another consideration of the multi - shot ablation threshold calculation by logarithmic dependence of the ablation rate d on the laser fluence. The morphological surface changes of the modified regions were characterized by scanning electron microscopy to estimate the generated variations after the laser treatment.

Ultrahigh Error Threshold for Surface Codes with Biased Noise

NASA Astrophysics Data System (ADS)

Tuckett, David K.; Bartlett, Stephen D.; Flammia, Steven T.

2018-02-01

We show that a simple modification of the surface code can exhibit an enormous gain in the error correction threshold for a noise model in which Pauli Z errors occur more frequently than X or Y errors. Such biased noise, where dephasing dominates, is ubiquitous in many quantum architectures. In the limit of pure dephasing noise we find a threshold of 43.7(1)% using a tensor network decoder proposed by Bravyi, Suchara, and Vargo. The threshold remains surprisingly large in the regime of realistic noise bias ratios, for example 28.2(2)% at a bias of 10. The performance is, in fact, at or near the hashing bound for all values of the bias. The modified surface code still uses only weight-4 stabilizers on a square lattice, but merely requires measuring products of Y instead of Z around the faces, as this doubles the number of useful syndrome bits associated with the dominant Z errors. Our results demonstrate that large efficiency gains can be found by appropriately tailoring codes and decoders to realistic noise models, even under the locality constraints of topological codes.

Instructions for the Tier I Emergency and Hazardous Chemical Inventory Form

EPA Pesticide Factsheets

The purpose of the Emergency Planning and Community Right-to-Know Act Tier I form is to provide State and local officials and the public with information on the general chemical hazard types and locations at your facility, if above reporting thresholds.

Deriving Predicted No-Effect Concentrations in Diverse Geographies for use in eco-TTC Estimations

EPA Science Inventory

cological Thresholds for Toxicologic Concern (eco-TTC) employs an assessment of distributions of Predicted No-Effect Concentrations (PNECs) for compounds following chemical grouping. Grouping can be by mode of action, structural fragments, or by chemical functional use. Thus, eco...

Diagnostics of microwave assisted electron cyclotron resonance plasma source for surface modification of nylon 6

NASA Astrophysics Data System (ADS)

More, Supriya E.; Das, Partha Sarathi; Bansode, Avinash; Dhamale, Gayatri; Ghorui, S.; Bhoraskar, S. V.; Sahasrabudhe, S. N.; Mathe, Vikas L.

2018-01-01

Looking at the increasing scope of plasma processing of materials surface, here we present the development and diagnostics of a microwave assisted Electron Cyclotron Resonance (ECR) plasma system suitable for surface modification of polymers. Prior to the surface-treatment, a detailed diagnostic mapping of the plasma parameters throughout the reactor chamber was carried out by using single and double Langmuir probe measurements in Ar plasma. Conventional analysis of I-V curves as well as the elucidation form of the Electron Energy Distribution Function (EEDF) has become the source of calibration of plasma parameters in the reaction chamber. The high energy tail in the EEDF of electron temperature is seen to extend beyond 60 eV, at much larger distances from the ECR zone. This proves the suitability of the rector for plasma processing, since the electron energy is much beyond the threshold energy of bond breaking in most of the polymers. Nylon 6 is used as a representative candidate for surface processing in the presence of Ar, H2 + N2, and O2 plasma, treated at different locations inside the plasma chamber. In a typical case, the work of adhesion is seen to almost get doubled when treated with oxygen plasma. Morphology of the plasma treated surface and its hydrophilicity are discussed in view of the variation in electron density and electron temperature at these locations. Nano-protrusions arising from plasma treatment are set to be responsible for the hydrophobicity. Chemical sputtering and physical sputtering are seen to influence the surface morphology on account of sufficient electron energies and increased plasma potential.

Articles of protective clothing adapted for deflecting chemical permeation and methods therefor

DOEpatents

Vo-Dinh, Tuan

1996-01-01

Apparatus and methods for detecting the permeation of hazardous or toxic chemicals through protective clothing are disclosed. The hazardous or toxic chemicals of interest do not possess the spectral characteristic of luminescence. The apparatus and methods utilize a spectrochemical modification technique to detect the luminescence quenching of an indicator compound which upon permeation of the chemical through the protective clothing, the indicator is exposed to the chemical, thus indicating chemical permeation.

Chemical Modifications that Affect Nutritional and Functional Properties of Proteins.

ERIC Educational Resources Information Center

Richardson, T.; Kester, J. J.

1984-01-01

Discusses chemical alterations of selected amino acids resulting from environmental effects (photooxidations, pH extremes, thermally induced effects). Also dicusses use of intentional chemical derivatizations of various functional groups in amino acid residue side chains and how recombinant DNA techniques might be useful in structure/function…

Triacetic acid lactone production from Saccharomyces cerevisiae

USDA-ARS?s Scientific Manuscript database

Triacetic acid lactone (TAL) is a potential platform chemical produced from acetyl-CoA and malonyl-CoA by the Gerbera hybrida 2-pyrone synthase (2PS) gene. Studies are ongoing to optimize production, purification, and chemical modification of TAL, which can be used to create the commercial chemicals...

Chemical modification of nanocellulose with canola oil fatty acid methyl ester

Treesearch

Liqing Wei; Umesh P. Agarwal; Kolby C. Hirth; Laurent M. Matuana; Ronald C. Sabo; Nicole M. Stark

2017-01-01

Cellulose nanocrystals (CNCs), produced from dissolving wood pulp, were chemically functionalized by transesterification with canola oil fatty acid methyl ester (CME). CME performs as both the reaction reagent and solvent. Transesterified CNC (CNCFE) was characterized for their chemical structure, morphology, crystalline structure, thermal stability, and hydrophobicity...

Determining the Location of DNA Modification and Mutation Caused by UVB Light in Skin Cancer

DTIC Science & Technology

2013-09-01

we obtain cleavage patterns consistent with the administered UV dosage and that sequencing libraries generated for both yeast and human cells show...understanding the mutations they cause. 15. SUBJECT TERMS UV DNA modification, HeLa cells, Skin Cancer 16. SECURITY CLASSIFICATION OF: 17...of mutations that are caused by UV light in cells and correlate them to modification frequencies. Understanding the initial chemical changes

Effects of covalent modification by 4-hydroxy-2-nonenal on the noncovalent oligomerization of ubiquitin.

PubMed

Grasso, Giuseppe; Axelsen, Paul H

2017-01-01

When lipid membranes containing ω-6 polyunsaturated fatty acyl chains are subjected to oxidative stress, one of the reaction products is 4-hydroxy-2-nonenal (HNE)-a chemically reactive short chain alkenal that can covalently modify proteins. The ubiquitin proteasome system is involved in the clearing of proteins modified by oxidation products such as HNE, but the chemical structure, stability and function of ubiquitin may be impaired by HNE modification. To evaluate this possibility, the susceptibility of ubiquitin to modification by HNE has been characterized over a range of concentrations where ubiquitin forms non-covalent oligomers. Results indicate that HNE modifies ubiquitin at only two of the many possible sites, and that HNE modification at these two sites alters the ubiquitin oligomerization equilibrium. These results suggest that any role ubiquitin may have in clearing proteins damaged by oxidative stress may itself be impaired by oxidative lipid degradation products. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Integrating real-time subsurface hydrologic monitoring with empirical rainfall thresholds to improve landslide early warning

USGS Publications Warehouse

Mirus, Benjamin B.; Becker, Rachel E.; Baum, Rex L.; Smith, Joel B.

2018-01-01

Early warning for rainfall-induced shallow landsliding can help reduce fatalities and economic losses. Although these commonly occurring landslides are typically triggered by subsurface hydrological processes, most early warning criteria rely exclusively on empirical rainfall thresholds and other indirect proxies for subsurface wetness. We explore the utility of explicitly accounting for antecedent wetness by integrating real-time subsurface hydrologic measurements into landslide early warning criteria. Our efforts build on previous progress with rainfall thresholds, monitoring, and numerical modeling along the landslide-prone railway corridor between Everett and Seattle, Washington, USA. We propose a modification to a previously established recent versus antecedent (RA) cumulative rainfall thresholds by replacing the antecedent 15-day rainfall component with an average saturation observed over the same timeframe. We calculate this antecedent saturation with real-time telemetered measurements from five volumetric water content probes installed in the shallow subsurface within a steep vegetated hillslope. Our hybrid rainfall versus saturation (RS) threshold still relies on the same recent 3-day rainfall component as the existing RA thresholds, to facilitate ready integration with quantitative precipitation forecasts. During the 2015–2017 monitoring period, this RS hybrid approach has an increase of true positives and a decrease of false positives and false negatives relative to the previous RA rainfall-only thresholds. We also demonstrate that alternative hybrid threshold formats could be even more accurate, which suggests that further development and testing during future landslide seasons is needed. The positive results confirm that accounting for antecedent wetness conditions with direct subsurface hydrologic measurements can improve thresholds for alert systems and early warning of rainfall-induced shallow landsliding.

Compressively sampled MR image reconstruction using generalized thresholding iterative algorithm

NASA Astrophysics Data System (ADS)

Elahi, Sana; kaleem, Muhammad; Omer, Hammad

2018-01-01

Compressed sensing (CS) is an emerging area of interest in Magnetic Resonance Imaging (MRI). CS is used for the reconstruction of the images from a very limited number of samples in k-space. This significantly reduces the MRI data acquisition time. One important requirement for signal recovery in CS is the use of an appropriate non-linear reconstruction algorithm. It is a challenging task to choose a reconstruction algorithm that would accurately reconstruct the MR images from the under-sampled k-space data. Various algorithms have been used to solve the system of non-linear equations for better image quality and reconstruction speed in CS. In the recent past, iterative soft thresholding algorithm (ISTA) has been introduced in CS-MRI. This algorithm directly cancels the incoherent artifacts produced because of the undersampling in k -space. This paper introduces an improved iterative algorithm based on p -thresholding technique for CS-MRI image reconstruction. The use of p -thresholding function promotes sparsity in the image which is a key factor for CS based image reconstruction. The p -thresholding based iterative algorithm is a modification of ISTA, and minimizes non-convex functions. It has been shown that the proposed p -thresholding iterative algorithm can be used effectively to recover fully sampled image from the under-sampled data in MRI. The performance of the proposed method is verified using simulated and actual MRI data taken at St. Mary's Hospital, London. The quality of the reconstructed images is measured in terms of peak signal-to-noise ratio (PSNR), artifact power (AP), and structural similarity index measure (SSIM). The proposed approach shows improved performance when compared to other iterative algorithms based on log thresholding, soft thresholding and hard thresholding techniques at different reduction factors.

Toxicological features of maleilated polyflavonoids from Pinus radiata (D. Don.) as potential functional additives for biomaterials design.

PubMed

García, Danny E; Medina, Paulina A; Zúñiga, Valentina I

2017-11-01

Polyflavonoids from Pinus radiata (D. Don.) are an abundant natural oligomers highly desirable as renewable chemicals. However, structural modification of polyflavonoids is a viable strategy in order to use such polyphenols as macrobuilding-blocks for biomaterial design. Polyflavonoids were esterified with three five-member cyclic anhydrides (maleic, itaconic, and citraconic) at 20 °C during 24 h in order to diversify physicochemical-, and biological-properties for agricultural, and food-packaging applications. In addition, the influence of the chemical modification, as well as the chemical structure of the grafting on toxicological features was evaluated. Structural features of derivatives were analyzed by spectroscopy (FT-IR and 1 H-NMR), and the degree of substitution was calculated. Toxicological profile was assessed by using three target species in a wide range of concentration (0.01-100 mgL - 1 ). Effect of polyflavonoids on the growth rate (Selenastrum capricornutum), mortality (Daphnia magna), and germination and radicle length (Lactuca sativa) was determined. Chemical modification affects the toxicological profile on the derivatives in a high extent. Results described remarkable differences in function of the target specie. The bioassays indicate differences of the polyflavonoids toxicological profile associated to the chemical structure of the grafting. Results allowed conclude that polyflavonoids from pine bark show slight toxic properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Climate-driven thresholds for chemical weathering in postglacial soils of New Zealand

NASA Astrophysics Data System (ADS)

Dixon, Jean L.; Chadwick, Oliver A.; Vitousek, Peter M.

2016-09-01

Chemical weathering in soils dissolves and alters minerals, mobilizes metals, liberates nutrients to terrestrial and aquatic ecosystems, and may modulate Earth's climate over geologic time scales. Climate-weathering relationships are often considered fundamental controls on the evolution of Earth's surface and biogeochemical cycles. However, surprisingly little consensus has emerged on if and how climate controls chemical weathering, and models and data from published literature often give contrasting correlations and predictions for how weathering rates and climate variables such as temperature or moisture are related. Here we combine insights gained from the different approaches, methods, and theory of the soil science, biogeochemistry, and geomorphology communities to tackle the fundamental question of how rainfall influences soil chemical properties. We explore climate-driven variations in weathering and soil development in young, postglacial soils of New Zealand, measuring soil elemental geochemistry along a large precipitation gradient (400-4700 mm/yr) across the Waitaki basin on Te Waipounamu, the South Island. Our data show a strong climate imprint on chemical weathering in these young soils. This climate control is evidenced by rapid nonlinear changes along the gradient in total and exchangeable cations in soils and in the increased movement and redistribution of metals with rainfall. The nonlinear behavior provides insight into why climate-weathering relationships may be elusive in some landscapes. These weathering thresholds also have significant implications for how climate may influence landscape evolution and the release of rock-derived nutrients to ecosystems, as landscapes that transition to wetter climates across this threshold may weather and deplete rapidly.

Reference guide to odor thresholds for hazardous air pollutants listed in the Clean Air Act amendments of 1990

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cain, W.S.; Shoaf, C.R.; Velasquez, S.F.

1992-03-01

In response to numerous requests for information related to odor thresholds, this document was prepared by the Air Risk Information Support Center in its role in providing technical assistance to State and Local government agencies on risk assessment of air pollutants. A discussion of basic concepts related to olfactory function and the measurement of odor thresholds is presented. A detailed discussion of criteria which are used to evaluate the quality of published odor threshold values is provided. The use of odor threshold information in risk assessment is discussed. The results of a literature search and review of odor threshold informationmore » for the chemicals listed as hazardous air pollutants in the Clean Air Act amendments of 1990 is presented. The published odor threshold values are critically evaluated based on the criteria discussed and the values of acceptable quality are used to determine a geometric mean or best estimate.« less

Carbon deposition thresholds on nickel-based solid oxide fuel cell anodes II. Steam:carbon ratio and current density

NASA Astrophysics Data System (ADS)

Kuhn, J.; Kesler, O.

2015-03-01

For the second part of a two part publication, coking thresholds with respect to molar steam:carbon ratio (SC) and current density in nickel-based solid oxide fuel cells were determined. Anode-supported button cell samples were exposed to 2-component and 5-component gas mixtures with 1 ≤ SC ≤ 2 and zero fuel utilization for 10 h, followed by measurement of the resulting carbon mass. The effect of current density was explored by measuring carbon mass under conditions known to be prone to coking while increasing the current density until the cell was carbon-free. The SC coking thresholds were measured to be ∼1.04 and ∼1.18 at 600 and 700 °C, respectively. Current density experiments validated the thresholds measured with respect to fuel utilization and steam:carbon ratio. Coking thresholds at 600 °C could be predicted with thermodynamic equilibrium calculations when the Gibbs free energy of carbon was appropriately modified. Here, the Gibbs free energy of carbon on nickel-based anode support cermets was measured to be -6.91 ± 0.08 kJ mol-1. The results of this two part publication show that thermodynamic equilibrium calculations with appropriate modification to the Gibbs free energy of solid-phase carbon can be used to predict coking thresholds on nickel-based anodes at 600-700 °C.

Enhanced understanding of the relationship between chemical modification and mechanical properties of wood

Treesearch

Charles R. Frihart; Daniel J. Yelle; John Ralph; Robert J. Moon; Donald S. Stone; Joseph E. Jakes

2008-01-01

Chemical additions to wood often change its bulk properties, which can be determined using conventional macroscopic mechanical tests. However, the controlling interactions between chemicals and wood take place at and below the scale of individual cells and cell walls. To better understand the effects of chemical additions to wood, we have adapted and extended two...

Martin Award Paper: Development of Interactive Virtual Laboratories to Help Students Learn Difficult Concepts in Thermodynamics

ERIC Educational Resources Information Center

Bowen, Alec S.; Reid, Daniel R.; Koretsky, Milo D.

2015-01-01

In this project, we explore the use of threshold concept theory as a design basis for development of Interactive Virtual Laboratories in thermodynamics. Thermodynamics is a difficult subject for chemical and biological engineering students to master. One reason for the difficulty is the diverse and challenging set of threshold concepts that they…

Migraine, arousal and sleep deprivation: comment on: "sleep quality, arousal and pain thresholds in migraineurs: a blinded controlled polysomnographic study".

PubMed

Vollono, Catello; Testani, Elisa; Losurdo, Anna; Mazza, Salvatore; Della Marca, Giacomo

2013-06-10

We discuss the hypothesis proposed by Engstrom and coworkers that Migraineurs have a relative sleep deprivation, which lowers the pain threshold and predispose to attacks. Previous data indicate that Migraineurs have a reduction of Cyclic Alternating Pattern (CAP), an essential mechanism of NREM sleep regulation which allows to dump the effect of incoming disruptive stimuli, and to protect sleep. The modifications of CAP observed in Migraineurs are similar to those observed in patients with impaired arousal (narcolepsy) and after sleep deprivation. The impairment of this mechanism makes Migraineurs more vulnerable to stimuli triggering attacks during sleep, and represents part of a more general vulnerability to incoming stimuli.

AGONISTIC SENSORY EFFECTS OF AIRBORNE CHEMICALS IN MIXTURES: ODOR, NASAL PUNGENCY, AND EYE IRRITATION

EPA Science Inventory

Threshold responses of odor, nasal pungency (irritation), and eye irritation were measured for single chemicals (1-propanol, 1-hexanol, ethyl acetate, heptyl acetate, 2-pentanone, 2-heptanone, toluene, ethyl benzene, and propyl benzene) and mixtures of them (two three-component m...

Identification of Maillard reaction induced chemical modifications on Ara h 1

USDA-ARS?s Scientific Manuscript database

The Maillard reaction is a non-enzymatic glycation reaction between proteins and reducing sugars that can modify nut allergens during thermal processing. These modifications can alter the structural and immunological properties of these allergens, and may result in increased IgE binding. Here, we ...

Encoded libraries of chemically modified peptides.

PubMed

Heinis, Christian; Winter, Greg

2015-06-01

The use of powerful technologies for generating and screening DNA-encoded protein libraries has helped drive the development of proteins as pharmaceutical ligands. However the development of peptides as pharmaceutical ligands has been more limited. Although encoded peptide libraries are typically several orders of magnitude larger than classical chemical libraries, can be more readily screened, and can give rise to higher affinity ligands, their use as pharmaceutical ligands is limited by their intrinsic properties. Two of the intrinsic limitations include the rotational flexibility of the peptide backbone and the limited number (20) of natural amino acids. However these limitations can be overcome by use of chemical modification. For example, the libraries can be modified to introduce topological constraints such as cyclization linkers, or to introduce new chemical entities such as small molecule ligands, fluorophores and photo-switchable compounds. This article reviews the chemistry involved, the properties of the peptide ligands, and the new opportunities offered by chemical modification of DNA-encoded peptide libraries. Copyright © 2015. Published by Elsevier Ltd.

Articles of protective clothing adapted for deflecting chemical permeation and methods there for

DOEpatents

Vo-Dinh, T.

1996-02-27

Apparatus and methods for detecting the permeation of hazardous or toxic chemicals through protective clothing are disclosed. The hazardous or toxic chemicals of interest do not possess the spectral characteristic of luminescence. The apparatus and methods utilize a spectrochemical modification technique to detect the luminescence quenching of an indicator compound which upon permeation of the chemical through the protective clothing, the indicator is exposed to the chemical, thus indicating chemical permeation. 12 figs.

Surface modification of polymers for biocompatibility via exposure to extreme ultraviolet radiation.

PubMed

Inam Ul Ahad; Bartnik, Andrzej; Fiedorowicz, Henryk; Kostecki, Jerzy; Korczyc, Barbara; Ciach, Tomasz; Brabazon, Dermot

2014-09-01

Polymeric biomaterials are being widely used for the treatment of various traumata, diseases and defects in human beings due to ease in their synthesis. As biomaterials have direct interaction with the extracellular environment in the biological world, biocompatibility is a topic of great significance. The introduction or enhancement of biocompatibility in certain polymers is still a challenge to overcome. Polymer biocompatibility can be controlled by surface modification. Various physical and chemical methods (e.g., chemical and plasma treatment, ion implantation, and ultraviolet irradiation etc.) are in use or being developed for the modification of polymer surfaces. However an important limitation in their employment is the alteration of bulk material. Different surface and bulk properties of biomaterials are often desirable for biomedical applications. Because extreme ultraviolet (EUV) radiation penetration is quite limited even in low density mediums, it could be possible to use it for surface modification without influencing the bulk material. This article reviews the degree of biocompatibility of different polymeric biomaterials being currently employed in various biomedical applications, the surface properties required to be modified for biocompatibility control, plasma and laser ablation based surface modification techniques, and research studies indicating possible use of EUV for enhancing biocompatibility. © 2013 Wiley Periodicals, Inc.

Sol–gel synthesis of MCM-41 silicas and selective vapor-phase modification of their surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roik, N.V., E-mail: roik_nadya@ukr.net; Belyakova, L.A.

2013-11-15

Silica particles with uniform hexagonal mesopore architecture were synthesized by template directed sol–gel condensation of tetraethoxysilane or mixture of tetraethoxysilane and (3-chloropropyl)triethoxysilane in a water–ethanol–ammonia solution. Selective functionalization of exterior surface of parent materials was carried out by postsynthetic treatment of template-filled MCM-41 and Cl-MCM-41 with vapors of (3-chloropropyl)triethoxysilane and 1,2-ethylenediamine in vacuum. The chemical composition of obtained mesoporous silicas was estimated by IR spectroscopy and chemical analysis of surface products of reactions. Characteristics of porous structure of resulting materials were determined from the data of X-ray, low-temperature nitrogen ad-desorption and transmission electron microscopy measurements. Obtained results confirm invariability ofmore » highly ordered mesoporous structure of MCM-41 and Cl-MCM-41 after their selective postsynthetic modification in vapor phase. It was proved that proposed method of vapor-phase functionalization of template-filled starting materials is not accompanied by dissolution of the template and chemical modification of pores surface. This provides preferential localization of grafted functional groups onto the exterior surface of mesoporous silicas. - Graphical abstract: Sol–gel synthesis and postsynthetic chemical modification of template-filled MCM-41 and Cl-MCM-41 with (3-chloropropyl)triethoxysilane and 1,2-ethylenediamine in vapor phase. Display Omitted - Highlights: • Synthesis of MCM-41 silica by template directed sol–gel condensation. • Selective vapor-phase functionalization of template-filled silica particles. • Preferential localization of grafted groups onto the exterior surface of mesoporous silicas.« less

Wetting in Color

NASA Astrophysics Data System (ADS)

Burgess, Ian Bruce

Colorimetric litmus tests such as pH paper have enjoyed wide commercial success due to their inexpensive production and exceptional ease of use. However, expansion of colorimetry to new sensing paradigms is challenging because macroscopic color changes are seldom coupled to arbitrary differences in the physical/chemical properties of a system. In this thesis I present in detail the development of Wetting in Color Technology, focusing primarily on its application as an inexpensive and highly selective colorimetric indicator for organic liquids. The technology exploits chemically-encoded inverse-opal photonic crystals to control the infiltration of fluids to liquid-specific spatial patterns, projecting minute differences in liquids' wettability to macroscopically distinct, easy-to-visualize structural color patterns. It is shown experimentally and corroborated with theoretical modeling using percolation theory that the high selectivity of wetting, upon-which the sensitivity of the indicator relies, is caused by the highly symmetric structure of our large-area, defect-free SiO2 inverse-opals. The regular structure also produces a bright iridescent color, which disappears when infiltrated with liquid - naturally coupling the optical and fluidic responses. Surface modification protocols are developed, requiring only silanization and selective oxidation, to facilitate the deterministic design of an indicator that differentiates a broad range of liquids. The resulting tunable, built-in horizontal and vertical chemistry gradients allow the wettability threshold to be tailored to specific liquids across a continuous range, and make the readout rely only on countable color differences. As wetting is a generic fluidic phenomenon, Wetting in Color technology could be suitable for applications in authentication or identification of unknown liquids across a broad range of industries. However, the generic nature of the response also ensures chemical non-specificity. It is shown that combinatorial measurements from an array of indicators add a degree of chemical specificity to the platform, which can be further improved by monitoring the drying of the inverse-opal films. While colorimetry is the central focus of this thesis, applications of this platform in encryption, fluidics and nanofabrication are also briefly explored.

Novel Insights Linking Ecological Health to Biogeochemical Hotspots across the Groundwater-Surface Water Interface in Mixed Land Use Stream Systems

NASA Astrophysics Data System (ADS)

McKnight, U. S.; Sonne, A. T.; Rasmussen, J. J.; Rønde, V.; Traunspurger, W.; Höss, S.; Bjerg, P. L.

2017-12-01

Increasing modifications in land use and water management have resulted in multiple stressors impacting freshwater ecosystems globally. Chemicals with the potential to impact aquatic habitats are still often evaluated individually for their adverse effects on ecosystem health. This may lead to critical underestimations of the combined impact caused by interactions occurring between stressors not typically evaluated together, e.g. xenobiotic groundwater pollutants and trace metals. To address this issue, we identified sources and levels of chemical stressors along a 16-km groundwater-fed stream corridor (Grindsted, Denmark), representative for a mixed land use stream system. Potential pollution sources included two contaminated sites (factory, landfill), aquaculture, wastewater/industrial discharges, and diffuse sources from agriculture and urban areas. Ecological status was determined by monitoring meiobenthic and macrobenthic invertebrate communities.The stream was substantially impaired by both geogenic and anthropogenic sources of metals throughout the investigated corridor, with concentrations close to or above threshold values for barium, copper, lead, nickel and zinc in the stream water, hyporheic zone and streambed sediment. The groundwater plume from the factory site caused elevated concentrations of chlorinated ethenes, benzene and pharmaceuticals in both the hyporheic zone and stream, persisting for several km downstream. Impaired ecological conditions, represented by a lower abundance of meiobenthic individuals, were found in zones where the groundwater plume discharges to the stream. The effect was only pronounced in areas characterized by high xenobiotic organic concentrations and elevated dissolved iron and arsenic levels - linked to the dissolution of iron hydroxides caused by the degradation of xenobiotic compounds in the plume. The results thus provide ecological evidence for the interaction of organic and inorganic chemical stressors, which may provide a missing link enabling the reconnection of chemical and ecological findings. This study highlights the importance of stream-aquifer interfaces for ecosystem functioning in terms of biological habitat, and that multiple stressor systems need to be tackled from a holistic perspective.

Wetting in color: colorimetric differentiation of organic liquids with high selectivity.

PubMed

Burgess, Ian B; Koay, Natalie; Raymond, Kevin P; Kolle, Mathias; Lončar, Marko; Aizenberg, Joanna

2012-02-28

Colorimetric litmus tests such as pH paper have enjoyed wide commercial success due to their inexpensive production and exceptional ease of use. Expansion of colorimetry to new sensing paradigms is challenging because macroscopic color changes are seldom coupled to arbitrary differences in the physical/chemical properties of a system. Here we present in detail the design of a "Wetting In Color Kit" (WICK), an inexpensive and highly selective colorimetric indicator for organic liquids that exploits chemically encoded inverse-opal photonic crystals to project minute differences in liquids' wettability to macroscopically distinct, easy-to-visualize structural color patterns. We show experimentally and corroborate with theoretical modeling using percolation theory that the highly symmetric structure of our large-area, defect-free SiO(2) inverse-opal films leads to sharply defined threshold wettability for liquid infiltration, occurring at intrinsic contact angles near 20° with an estimated resolution smaller than 5°. The regular structure also produces a bright iridescent color, which disappears when infiltrated with liquid, naturally coupling the optical and fluidic responses. To deterministically design a WICK that differentiates a broad range of liquids, we introduced a nondestructive quality control procedure to regulate the pore structure and developed two new surface modification protocols, both requiring only silanization and selective oxidation. The resulting tunable, built-in horizontal and vertical chemistry gradients let us tailor the wettability threshold to specific liquids across a continuous range. With patterned oxidation as a final step, we control the shape of the liquid-specific patterns displayed, making WICK easier to read. Using these techniques, we demonstrate the applicability of WICKs in several exemplary systems that colorimetrically distinguish (i) ethanol-water mixtures varying by only 2.5% in concentration; (ii) methanol, ethanol, and isopropyl alcohol; (iii) hexane, heptane, octane, nonane, and decane; and (iv) samples of gasoline (regular unleaded) and diesel. As wetting is a generic fluidic phenomenon, we envision that WICK could be suitable for applications in authentication or identification of unknown liquids across a broad range of industries.

Modification of turbulent particle transport and intermittency by biased rotation in LAPD

NASA Astrophysics Data System (ADS)

Dove, J.; Carter, T. A.; Maggs, J. E.

2006-10-01

The edge plasma in LAPD is rotated through the application of a bias voltage between the plasma source cathode and the vacuum vessel wall. As the bias voltage is applied and increased past a threshold value, the measured density profile steepens dramatically (from Ln> 10 ρs to Ln˜2 ρs) at a radius near the peak of the flow shear. Turbulent transport flux measurements in this region show that the flux is reduced and then suppressed completely as the threshold is approached. The amplitude of the density and azimuthal electric field fluctuations is observed to decrease during biased rotation, the product of the amplitudes decreasing by a factor of 5. However the dominant change appears in the cross-phase, which is altered dramatically, leading to the observed suppression and reversal of the turbulent flux. Detailed two-dimensional turbulent correlation measurements have been performed. During biased rotation, a dramatic increase in the azimuthal correlation is observed, however there is little change in the radial correlation length. An investigation of the modification of intermittent (or ``blobby'') transport due to the shear flow is underway and initial results will be presented.

Lessons from an evolving rRNA: 16S and 23S rRNA structures from a comparative perspective

NASA Technical Reports Server (NTRS)

Gutell, R. R.; Larsen, N.; Woese, C. R.

1994-01-01

The 16S and 23S rRNA higher-order structures inferred from comparative analysis are now quite refined. The models presented here differ from their immediate predecessors only in minor detail. Thus, it is safe to assert that all of the standard secondary-structure elements in (prokaryotic) rRNAs have been identified, with approximately 90% of the individual base pairs in each molecule having independent comparative support, and that at least some of the tertiary interactions have been revealed. It is interesting to compare the rRNAs in this respect with tRNA, whose higher-order structure is known in detail from its crystal structure (36) (Table 2). It can be seen that rRNAs have as great a fraction of their sequence in established secondary-structure elements as does tRNA. However, the fact that the former show a much lower fraction of identified tertiary interactions and a greater fraction of unpaired nucleotides than the latter implies that many of the rRNA tertiary interactions remain to be located. (Alternatively, the ribosome might involve protein-rRNA rather than intramolecular rRNA interactions to stabilize three-dimensional structure.) Experimental studies on rRNA are consistent to a first approximation with the structures proposed here, confirming the basic assumption of comparative analysis, i.e., that bases whose compositions strictly covary are physically interacting. In the exhaustive study of Moazed et al. (45) on protection of the bases in the small-subunit rRNA against chemical modification, the vast majority of bases inferred to pair by covariation are found to be protected from chemical modification, both in isolated small-subunit rRNA and in the 30S subunit. The majority of the tertiary interactions are reflected in the chemical protection data as well (45). On the other hand, many of the bases not shown as paired in Fig. 1 are accessible to chemical attack (45). However, in this case a sizeable fraction of them are also protected against chemical modification (in the isolated rRNA), which suggests that considerable higher-order structure remains to be found (although all of it may not involve base-base interactions and so may not be detectable by comparative analysis). The agreement between the higher-order structure of the small-subunit rRNA and protection against chemical modification is not perfect, however; some bases shown to covary canonically are accessible to chemical modification (45).(ABSTRACT TRUNCATED AT 400 WORDS).

Optimal Design for the Precise Estimation of an Interaction Threshold: The Impact of Exposure to a Mixture of 18 Polyhalogenated Aromatic Hydrocarbons

PubMed Central

Yeatts, Sharon D.; Gennings, Chris; Crofton, Kevin M.

2014-01-01

Traditional additivity models provide little flexibility in modeling the dose–response relationships of the single agents in a mixture. While the flexible single chemical required (FSCR) methods allow greater flexibility, its implicit nature is an obstacle in the formation of the parameter covariance matrix, which forms the basis for many statistical optimality design criteria. The goal of this effort is to develop a method for constructing the parameter covariance matrix for the FSCR models, so that (local) alphabetic optimality criteria can be applied. Data from Crofton et al. are provided as motivation; in an experiment designed to determine the effect of 18 polyhalogenated aromatic hydrocarbons on serum total thyroxine (T4), the interaction among the chemicals was statistically significant. Gennings et al. fit the FSCR interaction threshold model to the data. The resulting estimate of the interaction threshold was positive and within the observed dose region, providing evidence of a dose-dependent interaction. However, the corresponding likelihood-ratio-based confidence interval was wide and included zero. In order to more precisely estimate the location of the interaction threshold, supplemental data are required. Using the available data as the first stage, the Ds-optimal second-stage design criterion was applied to minimize the variance of the hypothesized interaction threshold. Practical concerns associated with the resulting design are discussed and addressed using the penalized optimality criterion. Results demonstrate that the penalized Ds-optimal second-stage design can be used to more precisely define the interaction threshold while maintaining the characteristics deemed important in practice. PMID:22640366

Chemical modification

Treesearch

R. M. Rowell

2004-01-01

Wood is a hygroscopic resource that was designed to perform, in nature, in a wet environment. Nature is programmed to recycle wood in a timely way through biological, thermal, aqueous, photochemical, chemical, and mechanical degradations. In simple terms, nature builds wood from carbon dioxide and water and has all the tools to recycle it back to the starting chemicals...

76 FR 76674 - Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or on Various...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-08

... Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or on Various Commodities AGENCY...: This document announces the Agency's receipt of several initial filings of pesticide petitions requesting the establishment or modification of regulations for residues of pesticide chemicals in or on...

Properties Characterization of Chemically Modified Hemp Hurds

PubMed Central

Stevulova, Nadezda; Cigasova, Julia; Estokova, Adriana; Terpakova, Eva; Geffert, Anton; Kacik, Frantisek; Singovszka, Eva; Holub, Marian

2014-01-01

The effect of chemical treatment of hemp hurds slices in three solutions (EDTA (Ethylenediaminetetraacetic acid), NaOH and Ca(OH)2) on the properties of natural material was discussed in this paper. Changes in the morphology, chemical composition and structure as well as thermal stability of hemp hurds before and after their modification were investigated by using FTIR (Fourier transform infrared spectroscopy), XRD (X-ray powder diffraction analysis) and TG (thermogravimetry)/DSC (differential scanning calorimetry). Size exclusion chromatography (SEC) measurements were used for determination of degree of cellulose polymerization of hemp hurd samples. Chemical modification is related to the partial removal of non-cellulosic components of lignin, hemicellulose and pectin as well as waxes from the surface of hemp hurd slices. Another effect of the chemical treatment applied is connected with increasing the crystallinity index of cellulose determined by FTIR and XRD methods. Decrease in degree of cellulose polymerization and polydispersity index in chemically modified hemp hurds compared to the original sample was observed. Increase in thermal stability of treated hemp hurd was found. The most significant changes were observed in alkaline treated hemp hurds by NaOH. PMID:28788294

Molecular Signaling Network Motifs Provide a Mechanistic Basis for Cellular Threshold Responses

PubMed Central

Bhattacharya, Sudin; Conolly, Rory B.; Clewell, Harvey J.; Kaminski, Norbert E.; Andersen, Melvin E.

2014-01-01

Background: Increasingly, there is a move toward using in vitro toxicity testing to assess human health risk due to chemical exposure. As with in vivo toxicity testing, an important question for in vitro results is whether there are thresholds for adverse cellular responses. Empirical evaluations may show consistency with thresholds, but the main evidence has to come from mechanistic considerations. Objectives: Cellular response behaviors depend on the molecular pathway and circuitry in the cell and the manner in which chemicals perturb these circuits. Understanding circuit structures that are inherently capable of resisting small perturbations and producing threshold responses is an important step towards mechanistically interpreting in vitro testing data. Methods: Here we have examined dose–response characteristics for several biochemical network motifs. These network motifs are basic building blocks of molecular circuits underpinning a variety of cellular functions, including adaptation, homeostasis, proliferation, differentiation, and apoptosis. For each motif, we present biological examples and models to illustrate how thresholds arise from specific network structures. Discussion and Conclusion: Integral feedback, feedforward, and transcritical bifurcation motifs can generate thresholds. Other motifs (e.g., proportional feedback and ultrasensitivity)produce responses where the slope in the low-dose region is small and stays close to the baseline. Feedforward control may lead to nonmonotonic or hormetic responses. We conclude that network motifs provide a basis for understanding thresholds for cellular responses. Computational pathway modeling of these motifs and their combinations occurring in molecular signaling networks will be a key element in new risk assessment approaches based on in vitro cellular assays. Citation: Zhang Q, Bhattacharya S, Conolly RB, Clewell HJ III, Kaminski NE, Andersen ME. 2014. Molecular signaling network motifs provide a mechanistic basis for cellular threshold responses. Environ Health Perspect 122:1261–1270; http://dx.doi.org/10.1289/ehp.1408244 PMID:25117432

Microchemical Pen: An Open Microreactor for Region-Selective Surface Modification.

PubMed

Mao, Sifeng; Sato, Chiho; Suzuki, Yuma; Yang, Jianmin; Zeng, Hulie; Nakajima, Hizuru; Yang, Ming; Lin, Jin-Ming; Uchiyama, Katsumi

2016-10-18

Various micro surface-modification approaches including photolithography, dip-pen lithography and ink-jet systems have been developed and used to extend the functionalities of solid surfaces. While those approaches work in the "open space", push-pull systems which work in solutions have recently drawn considerable attention. However, the confining flows performed by push-pull systems have realized only the dispense process, while microscale, region-selective chemical reactions have remained unattainable. This study reports a microchemical pen that enables region-selective chemical reactions for the micro surface modification/patterning. The chemical pen is based on the principle of microfluidic laminar flows and the resulting mixing of reagents by the mutual diffusion. The tiny diffusion layer performs as the working region. This report represents the first demonstration of an open microreactor in which two different reagents react on a real solid sample. The multifunctional characteristics of the microchemical pen are confirmed by different types of reactions in many research areas, including inorganic chemistry, polymer science, electrochemistry and biological sample treatment. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extensive Chemical Modifications in the Primary Protein Structure of IgG1 Subvisible Particles Are Necessary for Breaking Immune Tolerance.

PubMed

Boll, Björn; Bessa, Juliana; Folzer, Emilien; Ríos Quiroz, Anacelia; Schmidt, Roland; Bulau, Patrick; Finkler, Christof; Mahler, Hanns-Christian; Huwyler, Jörg; Iglesias, Antonio; Koulov, Atanas V

2017-04-03

A current concern with the use of therapeutic proteins is the likely presence of aggregates and submicrometer, subvisible, and visible particles. It has been proposed that aggregates and particles may lead to unwanted increases in the immune response with a possible impact on safety or efficacy. The aim of this study was thus to evaluate the ability of subvisible particles of a therapeutic antibody to break immune tolerance in an IgG1 transgenic mouse model and to understand the particle attributes that might play a role in this process. We investigated the immunogenic properties of subvisible particles (unfractionated, mixed populations, and well-defined particle size fractions) using a transgenic mouse model expressing a mini-repertoire of human IgG1 (hIgG1 tg). Immunization with proteinaceous subvisible particles generated by artificial stress conditions demonstrated that only subvisible particles bearing very extensive chemical modifications within the primary amino acid structure could break immune tolerance in the hIgG1 transgenic mouse model. Protein particles exhibiting low levels of chemical modification were not immunogenic in this model.

Chemical modifications and bioconjugate reactions of nanomaterials for sensing, imaging, drug delivery and therapy.

PubMed

Biju, Vasudevanpillai

2014-02-07

As prepared nanomaterials of metals, semiconductors, polymers and carbon often need surface modifications such as ligand exchange, and chemical and bioconjugate reactions for various biosensor, bioanalytical, bioimaging, drug delivery and therapeutic applications. Such surface modifications help us to control the physico-chemical, toxicological and pharmacological properties of nanomaterials. Furthermore, introduction of various reactive functional groups on the surface of nanomaterials allows us to conjugate a spectrum of contrast agents, antibodies, peptides, ligands, drugs and genes, and construct multifunctional and hybrid nanomaterials for the targeted imaging and treatment of cancers. This tutorial review is intended to provide an introduction to newcomers about how chemical and bioconjugate reactions transform the surface of nanomaterials such as silica nanoparticles, gold nanoparticles, gold quantum clusters, semiconductor quantum dots, carbon nanotubes, fullerene and graphene, and accordingly formulate them for applications such as biosensing, bioimaging, drug and gene delivery, chemotherapy, photodynamic therapy and photothermal therapy. Nonetheless, controversial reports and our growing concerns about toxicity and pharmacokinetics of nanomaterials suggest the need for not only rigorous in vivo experiments in animal models but also novel nanomaterials for practical applications in the clinical settings. Further reading of original and review articles cited herein is necessary to buildup in-depth knowledge about the chemistry, bioconjugate chemistry and biological applications of individual nanomaterials.

In vitro evaluation of digestive and endolysosomal enzymes to cleave CML-modified Ara h 1 peptides

USDA-ARS?s Scientific Manuscript database

The sensory, biological, chemical, and immunological characteristics of foods can be modified non-enzymatically during processing. Notably, these modifications may modulate the allergenic potency of food allergens, such as the Ara h 1 peanut allergen. Carboxymethyl-lysine (CML) modification is a p...

Chemical Modification of Papain and Subtilisin: An Active Site Comparison

ERIC Educational Resources Information Center

St-Vincent, Mireille; Dickman, Michael

2004-01-01

An experiment using methyle methanethiosulfonate (MMTS) and phenylmethylsulfonyl flouride (PMSF) to specifically modify the cysteine and serine residues in the active sites of papain and subtilism respectively is demonstrated. The covalent modification of these enzymes and subsequent rescue of papain shows the beginning biochemist that proteins…

Improvement of activity and stability of chloroperoxidase by chemical modification

PubMed Central

Liu, Jian-Zhong; Wang, Min

2007-01-01

Background Enzymes show relative instability in solvents or at elevated temperature and lower activity in organic solvent than in water. These limit the industrial applications of enzymes. Results In order to improve the activity and stability of chloroperoxidase, chloroperoxidase was modified by citraconic anhydride, maleic anhydride or phthalic anhydride. The catalytic activities, thermostabilities and organic solvent tolerances of native and modified enzymes were compared. In aqueous buffer, modified chloroperoxidases showed similar Km values and greater catalytic efficiencies kcat/Km for both sulfoxidation and oxidation of phenol compared to native chloroperoxidase. Of these modified chloroperoxidases, citraconic anhydride-modified chloroperoxidase showed the greatest catalytic efficiency in aqueous buffer. These modifications of chloroperoxidase increased their catalytic efficiencies for sulfoxidation by 12%~26% and catalytic efficiencies for phenol oxidation by 7%~53% in aqueous buffer. However, in organic solvent (DMF), modified chloroperoxidases had lower Km values and higher catalytic efficiencies kcat/Km than native chloroperoxidase. These modifications also improved their thermostabilities by 1~2-fold and solvent tolerances of DMF. CD studies show that these modifications did not change the secondary structure of chloroperoxidase. Fluorescence spectra proved that these modifications changed the environment of tryptophan. Conclusion Chemical modification of epsilon-amino groups of lysine residues of chloroperoxidase using citraconic anhydride, maleic anhydride or phthalic anhydride is a simple and powerful method to enhance catalytic properties of enzyme. The improvements of the activity and stability of chloroperoxidase are related to side chain reorientations of aromatics upon both modifications. PMID:17511866

Base modification strategies to modulate immune stimulation by an siRNA.

PubMed

Valenzuela, Rachel Anne P; Suter, Scott R; Ball-Jones, Alexi A; Ibarra-Soza, José M; Zheng, Yuxuan; Beal, Peter A

2015-01-19

Immune stimulation triggered by siRNAs is one of the major challenges in the development of safe RNAi-based therapeutics. Within an immunostimulatory siRNA sequence, this hurdle is commonly addressed by using ribose modifications (e.g., 2'-OMe or 2'-F), which results in decreased cytokine production. However, as immune stimulation by siRNAs is a sequence-dependent phenomenon, recognition of the nucleobases by the trigger receptor(s) is also likely. Here, we use the recently published crystal structures of Toll-like receptor 8 (TLR8) bound to small-molecule agonists to generate computational models for ribonucleotide binding by this immune receptor. Our modeling suggested that modification of either the Watson-Crick or Hoogsteen face of adenosine would disrupt nucleotide/TLR8 interactions. We employed chemical synthesis to alter either the Watson-Crick or Hoogsteen face of adenosine and evaluated the effect of these modifications in an siRNA guide strand by measuring the immunostimulatory and RNA interference properties. For the siRNA guide strand tested, we found that modifying the Watson-Crick face is generally more effective at blocking TNFα production in human peripheral blood mononuclear cells (PBMCs) than modification at the Hoogsteen edge. We also observed that modifications near the 5'-end were more effective at blocking cytokine production than those placed at the 3'-end. This work advances our understanding of how chemical modifications can be used to optimize siRNA performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical modification of chitosan for efficient gene therapy.

PubMed

Jiang, Hu-Lin; Cui, Peng-Fei; Xie, Rong-Lin; Cho, Chong-Su

2014-01-01

Gene therapy involves the introduction of foreign genetic material into cells in order to exert a therapeutic effect. Successful gene therapy relies on effective vector system. Viral vectors are highly efficient in transfecting cells, but the undesirable complications limit their therapeutic applications. As a natural biopolymer, chitosan has been considered to be a good gene carrier candidate due to its ideal character which combines biocompatibility, low toxicity with high cationic density together. However, the low cell specificity and low transfection efficiency of chitosan as a gene carrier need to be overcome before undertaking clinical trials. This chapter is principally on those endeavors such as chemical modifications using cell-specific ligands and stimuli-response groups as well as penetrating modifications that have been done to increase the performances of chitosan in gene therapy. © 2014 Elsevier Inc. All rights reserved.

Manipulating surface wettability and oil absorbency of diatomite depending on processing and ambient conditions

NASA Astrophysics Data System (ADS)

Özen, İlhan; Şimşek, Süleyman; Okyay, Gamze

2015-03-01

In this study, a diatomite sample, which is a natural inorganic mineral with inherently high water and oil absorption capacity, was subjected to grinding before surface modification. Afterwards, the diatomite surface was modified via facile methods using a fluorocarbon (FC) chemical and stearic acid (SA) in addition to the sol-gel fluorosilanization (FS) process. The water and oil wettability, and oil absorbency properties of the unmodified and modified diatomites were investigated in addition to diatomite characterizations such as chemical content, surface area, particle size distribution, morphology, and modification efficiency. It was revealed that the wettability was changed completely depending on the surface modification agent and the media used, while the oil absorbency property surprisingly did not change. On the other hand, the oil absorbency was worsened by the grinding process, whereas the wettability was not affected.

Chemical modification of the cocoa shell surface using diazonium salts.

PubMed

Fioresi, Flavia; Vieillard, Julien; Bargougui, Radhouane; Bouazizi, Nabil; Fotsing, Patrick Nkuigue; Woumfo, Emmanuel Djoufac; Brun, Nicolas; Mofaddel, Nadine; Le Derf, Franck

2017-05-15

The outer portion of the cocoa bean, also known as cocoa husk or cocoa shell (CS), is an agrowaste material from the cocoa industry. Even though raw CS is used as food additive, garden mulch, and soil conditioner or even burnt for fuel, this biomass material has hardly ever been investigated for further modification. This article proposes a strategy of chemical modification of cocoa shell to add value to this natural material. The study investigates the grafting of aryl diazonium salt on cocoa shell. Different diazonium salts were grafted on the shell surface and characterized by infrared spectroscopy and scanning electronic microscopy imaging. Strategies were developed to demonstrate the spontaneous grafting of aryl diazonium salt on cocoa shell and to elucidate that lignin is mainly involved in immobilizing the phenyl layer. Copyright © 2017 Elsevier Inc. All rights reserved.

Breast density quantification with cone-beam CT: A post-mortem study

PubMed Central

Johnson, Travis; Ding, Huanjun; Le, Huy Q.; Ducote, Justin L.; Molloi, Sabee

2014-01-01

Forty post-mortem breasts were imaged with a flat-panel based cone-beam x-ray CT system at 50 kVp. The feasibility of breast density quantification has been investigated using standard histogram thresholding and an automatic segmentation method based on the fuzzy c-means algorithm (FCM). The breasts were chemically decomposed into water, lipid, and protein immediately after image acquisition was completed. The percent fibroglandular volume (%FGV) from chemical analysis was used as the gold standard for breast density comparison. Both image-based segmentation techniques showed good precision in breast density quantification with high linear coefficients between the right and left breast of each pair. When comparing with the gold standard using %FGV from chemical analysis, Pearson’s r-values were estimated to be 0.983 and 0.968 for the FCM clustering and the histogram thresholding techniques, respectively. The standard error of the estimate (SEE) was also reduced from 3.92% to 2.45% by applying the automatic clustering technique. The results of the postmortem study suggested that breast tissue can be characterized in terms of water, lipid and protein contents with high accuracy by using chemical analysis, which offers a gold standard for breast density studies comparing different techniques. In the investigated image segmentation techniques, the FCM algorithm had high precision and accuracy in breast density quantification. In comparison to conventional histogram thresholding, it was more efficient and reduced inter-observer variation. PMID:24254317

Interaction of corneal nociceptive stimulation and lacrimal secretion.

PubMed

Situ, Ping; Simpson, Trefford L

2010-11-01

To investigate the interaction between corneal stimuli at different positions and tear secretion and to establish relationships between nociceptive stimuli detection thresholds and stimulated tearing. Using a computerized Belmonte-esthesiometer, mechanical and chemical stimuli, from 0% to 200% of the threshold in 50% steps, were delivered (in random order) to the central and peripheral (approximately 2-mm inside the limbus) cornea during four separate sessions to 15 subjects. Immediately after each stimulus, tear meniscus height (TMH) was measured using optical coherence tomography to quantify the amount of lacrimal secretion, and subjects reported whether they felt tears starting to accumulate in their eyes. Thresholds (50% detection) for detection of tearing were estimated. TMH increased with increasing stimulus intensity (P < 0.05), and the overall increase was higher with central stimulation than with peripheral stimulation (P < 0.05). The changes in TMH with threshold-scaled stimulus intensity depended on test location (P < 0.05) and stimulus modality (P < 0.05). The maximum intensity of mechanical stimulation of the central cornea induced the greatest TMH (all P < 0.05). For chemical stimulation, the stimulus intensity required to induce detectable tearing was higher than that required to detect a stimulus and higher in the periphery than at the center (all P < 0.05). Noxious mechanical and chemical stimuli evoked measurable tear secretion, with central corneal mechanical stimulation evoking the strongest lacrimation reflex. Central mechanical corneal stimulation is the most effective stimulus-position pairing and appears to be the major sensory driving force for reflex tear secretion by the lacrimal functional unit.

Theory and Experimental and Chemical Instabilities

DTIC Science & Technology

1989-01-31

Thresholds, Hysteresis, and Neuromodulation of Signal-to-Noise; and Statistical-Mechanical Theory of Many-body Effects in Reaction Rates. T Ic 2 UL3...submitted to the Journal of Physical Chemistry. 6. Noise in Neural Networks: Thresholds, Hysteresis, and Neuromodulation of Signal-to-Noise. We study a...neural-network model including Gaussian noise, higher-order neuronal interactions, and neuromodulation . For a first-order network, there is a

Apparatus and methods for detecting chemical permeation

DOEpatents

Vo-Dinh, T.

1994-12-27

Apparatus and methods for detecting the permeation of hazardous or toxic chemicals through protective clothing are disclosed. The hazardous or toxic chemicals of interest do not possess the spectral characteristic of luminescence. The apparatus and methods utilize a spectrochemical modification technique to detect the luminescence quenching of an indicator compound which upon permeation of the chemical through the protective clothing, the indicator is exposed to the chemical, thus indicating chemical permeation. The invention also relates to the fabrication of protective clothing materials. 13 figures.

Supramolecular engineering through temperature-induced chemical modification of 2H-tetraphenylporphyrin on Ag(111): flat phenyl conformation and possible dehydrogenation reactions.

PubMed

Di Santo, Giovanni; Blankenburg, Stephan; Castellarin-Cudia, Carla; Fanetti, Mattia; Borghetti, Patrizia; Sangaletti, Luigi; Floreano, Luca; Verdini, Alberto; Magnano, Elena; Bondino, Federica; Pignedoli, Carlo A; Nguyen, Manh-Thuong; Gaspari, Roberto; Passerone, Daniele; Goldoni, Andrea

2011-12-16

Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structures, properties, modifications, and uses of oat starch.

PubMed

Zhu, Fan

2017-08-15

There has been increasing interest to utilise oats and their components to formulate healthy food products. Starch is the major component of oat kernels and may account up to 60% of the dry weight. Starch properties may greatly determine the product quality. As a by-product of oat processing and fractionation, the starch may also be utilised for food and non-food applications. This mini-review updates the recent advances in the isolation, chemical and granular structures, physicochemical properties, chemical and physical modifications, and food and non-food uses of oat starch. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dopamine Polymerization in Liquid Marbles: A General Route to Janus Particle Synthesis.

PubMed

Sheng, Yifeng; Sun, Guanqing; Ngai, To

2016-04-05

Coating a liquid with a particle shell not only renders a droplet superhydrophobic but also isolates a well-confined microenvironment for miniaturized chemical processes. Previously, we have demonstrated that particles at the liquid marble interface provide an ideal platform for the site-selective modification of superhydrophobic particles. However, the need for a special chemical reaction limits their potential use for the fabrication of Janus particles with various properties. Herein, we combine the employment of liquid marbles as microreactors with the remarkable adhesive ability of polydopamine to develop a general route for the synthesis of Janus particles from micrometer-sized superhydrophobic particles. We demonstrate that dopamine polymerization and deposition inside liquid marbles could be used for the selective surface modification of microsized silica particles, resulting in the formation of Janus particles. Moreover, it is possible to manipulate the Janus balance of the particles via the addition of surfactants and/or organic solvents to tune the interfacial energy. More importantly, owing to the many functional groups in polydopamine, we show that versatile strategies could be introduced to use these partially polydopamine-coated silica particles as platforms for further modification, including nanoparticle immobilization, metal ion chelation and reduction, as well as for chemical reactions. Given the flexibility in the choice of cores and the modification strategies, this developed method is distinctive in its high universality, good controllability, and great practicability.

Investigation of surface halide modification of nitrile butadiene rubber

NASA Astrophysics Data System (ADS)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

Methods for improving the damage performance of fused silica polished by magnetorheological finishing

DOE PAGES

Kafka, Kyle R. P.; Hoffman, Brittany N.; Papernov, Semyon; ...

2017-12-11

The laser-induced damage threshold of fused-silica samples processed via magnetorheological finishing is investigated for polishing compounds depending on the type of abrasive material and the post-polishing surface roughness. The effectiveness of laser conditioning is examined using a ramped pre-exposure with the same 351-nm, 3-ns Gaussian pulses. Lastly, we examine chemical etching of the surface and correlate the resulting damage threshold to the etching protocol. A combination of etching and laser conditioning is found to improve the damage threshold by a factor of ~3, while maintaining <1-nm surface roughness.

Methods for improving the damage performance of fused silica polished by magnetorheological finishing

NASA Astrophysics Data System (ADS)

Kafka, K. R. P.; Hoffman, B.; Papernov, S.; DeMarco, M. A.; Hall, C.; Marshall, K. L.; Demos, S. G.

2017-12-01

The laser-induced damage threshold of fused-silica samples processed via magnetorheological finishing is investigated for polishing compounds depending on the type of abrasive material and the post-polishing surface roughness. The effectiveness of laser conditioning is examined using a ramped pre-exposure with the same 351-nm, 3-ns Gaussian pulses. Finally, we examine chemical etching of the surface and correlate the resulting damage threshold to the etching protocol. A combination of etching and laser conditioning is found to improve the damage threshold by a factor of 3, while maintaining <1-nm surface roughness.

Refining the threshold of toxicological concern (TTC) for risk prioritization of trace chemicals in food.

PubMed

Felter, Susan; Lane, Richard W; Latulippe, Marie E; Llewellyn, G Craig; Olin, Stephen S; Scimeca, Joseph A; Trautman, Thomas D

2009-09-01

Due to ever-improving analytical capabilities, very low levels of unexpected chemicals can now be detected in foods. Although these may be toxicologically insignificant, such incidents often garner significant attention. The threshold of toxicological concern (TTC) methodology provides a scientifically defensible, transparent approach for putting low-level exposures in the context of potential risk, as a tool to facilitate prioritization of responses, including potential mitigation. The TTC method supports the establishment of tiered, health-protective exposure limits for chemicals lacking a full toxicity database, based on evaluation of the known toxicity of chemicals which share similar structural characteristics. The approach supports the view that prudent actions towards public health protection are based on evaluation of safety as opposed to detection chemistry. This paper builds on the existing TTC literature and recommends refinements that address two key areas. The first describes the inclusion of genotoxicity data as a way to refine the TTC limit for chemicals that have structural alerts for genotoxicity. The second area addresses duration of exposure. Whereas the existing TTC exposure limits assume a lifetime of exposure, human exposure to unintended chemicals in food is often only for a limited time. Recommendations are made to refine the approach for less-than-lifetime exposures.

Influence of pyrolysis temperature on lead immobilization by chemically modified coconut fiber-derived biochars in aqueous environments.

PubMed

Wu, Weidong; Li, Jianhong; Niazi, Nabeel Khan; Müller, Karin; Chu, Yingchao; Zhang, Lingling; Yuan, Guodong; Lu, Kouping; Song, Zhaoliang; Wang, Hailong

2016-11-01

Biochar has received widespread attention as an eco-friendly and efficient material for immobilization of toxic heavy metals in aqueous environments. In the present study, three types of coconut fiber-derived biochars were obtained by pyrolyzing at three temperatures, i.e., 300, 500, and 700 °C. In addition, nine types of biochars were prepared by chemical modification with ammonia, hydrogen peroxide, and nitric acid, respectively, which were used to investigate changes in physico-chemical properties by inter alia, Fourier transformation infrared spectrophotometry (FTIR), scanning electron microscope (SEM), and BET specific surface area analysis. Batch sorption experiments were carried out to determine the sorption capacity of the biochars for lead (Pb) in aqueous solutions. Results showed that the cation exchange capacity of biochar pyrolyzed at 300 °C and modified with nitric acid increased threefold compared to the control. Loosely corrugated carbon surface and uneven carbon surface of the biochar pyrolyzed at 300 °C were produced during ammonia and nitric acid modifications. Removal rate of Pb by the coconut biochar pyrolyzed at 300 °C and modified with ammonia was increased from 71.8 to 99.6 % compared to the untreated biochar in aqueous solutions containing 100 mg L -1 Pb. However, chemical modification did not enhance adsorption of Pb of the biochars pyrolyzed at higher temperatures (e.g., 500 or 700 °C), indicating that resistance of biochars to chemical treatment increased with pyrolysis temperature.

Zinc Oxide—From Synthesis to Application: A Review

PubMed Central

Kołodziejczak-Radzimska, Agnieszka; Jesionowski, Teofil

2014-01-01

Zinc oxide can be called a multifunctional material thanks to its unique physical and chemical properties. The first part of this paper presents the most important methods of preparation of ZnO divided into metallurgical and chemical methods. The mechanochemical process, controlled precipitation, sol-gel method, solvothermal and hydrothermal method, method using emulsion and microemulsion enviroment and other methods of obtaining zinc oxide were classified as chemical methods. In the next part of this review, the modification methods of ZnO were characterized. The modification with organic (carboxylic acid, silanes) and inroganic (metal oxides) compounds, and polymer matrices were mainly described. Finally, we present possible applications in various branches of industry: rubber, pharmaceutical, cosmetics, textile, electronic and electrotechnology, photocatalysis were introduced. This review provides useful information for specialist dealings with zinc oxide. PMID:28788596

Chemical modification : a non-toxic approach to wood preservation

Treesearch

Roger M. Rowell

2006-01-01

Wood can be chemically modified to reduce the moisture content of the cell wall and increases decay resistance. As the level of bonded chemical increases, the cell wall equilibrium moisture content decreases and the resistance to attack by white-and brown-rot fungi increases. There is a direct relationship between the decrease in cell wall moisture Content and...

Truffles decontamination treatment by ionizing radiation

NASA Astrophysics Data System (ADS)

Adamo, M.; Capitani, D.; Mannina, L.; Cristinzio, M.; Ragni, P.; Tata, A.; Coppola, R.

2004-09-01

A research project, funded by the Italian Ministry of Research and the European Union, is in progress aimed to develop processes to enhance, by irradiation, the safety and the wholesomeness of fresh products relevant for Italian food industry. Irradiation was performed on truffles, since the bacterial contamination impairs their trade in foreign countries. The microbial population and the shelf life under refrigeration were studied either on samples untreated or on samples submitted to γ-rays in a 1-2.5 kGy dose range. The effect of the treatment was monitored by UV and NMR techniques. Total microbial population and the shelf life prolongation were investigated. The synergistic effect of the dose, the packaging under vacuum and the storage/irradiation temperature resulted in a direct effect on the microbial load, spoilage and shelf life. After the irradiation, small variations in the intensity of some NMR resonances due to aromatic compounds and other unassigned compounds were observed. As confirmed by UV spectrophotometric data, these phenomena seemed to originate from a small degradation of polyphenols; the induced growth of soluble phenols suggested that the 1.5 kGy dose can be considered as the radiation dose threshold beyond which clear chemical modifications on truffles appear.

Ablation and cone formation mechanism on CR-39 by ArF laser irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shakeri Jooybari, B., E-mail: baninshakery@gmail.com, E-mail: hafarideh@aut.ac.ir; Nuclear Science and Technology Research Institute NSRT, Tehran; Afarideh, H., E-mail: baninshakery@gmail.com, E-mail: hafarideh@aut.ac.ir

In this work, chemical properties, surface modification, and micro structures formation on ablated polyallyl di-glycol carbonate (CR-39) polymer by ArF laser irradiation (λ = 193 nm) at various fluences and pulse number were investigated. CR-39 samples have been irradiated with an ArF laser (193 nm) at a repetition rate of 1 Hz. Threshold fluence of ablation and effective absorption coefficient of CR-39 were determined. Conical microstructures (Taylor cone) formed on laser-ablated CR-39 exhibit: smooth, Taylor cone shape walls and sharp tips together with interference and well defined fringe-structure with a period of 230 nm, around cone base. Mechanism of cone formation and cone evolution of CR-39more » ablated surface were investigated by change of fluences (at a given pulse number) and pulse number (at a given fluence). Cone height, cone base, and region of interface were increased in micrometer steps by increasing the total fluence. Depression on the base of the cone and the circular fringe were simulated. FTIR spectra were measured and energy dispersive x-ray analysis of irradiated and un-irradiated samples was performed.« less

Micrometer scale spacings between fibronectin nanodots regulate cell morphology and focal adhesions

NASA Astrophysics Data System (ADS)

Horzum, Utku; Ozdil, Berrin; Pesen-Okvur, Devrim

2014-04-01

Cell adhesion to extracellular matrix is an important process for both health and disease states. Surface protein patterns that are topographically flat, and do not introduce other chemical, topographical or rigidity related functionality and, more importantly, that mimic the organization of the in vivo extracellular matrix are desired. Previous work showed that vinculin and cytoskeletal organization are modulated by size and shape of surface nanopatterns. However, quantitative analysis on cell morphology and focal adhesions as a function of micrometer scale spacings of FN nanopatterns was absent. Here, electron beam lithography was used to pattern fibronectin nanodots with micrometer scale spacings on a K-casein background on indium tin oxide coated glass which, unlike silicon, is transparent and thus suitable for many light microscopy techniques. Exposure times were significantly reduced using the line exposure mode with micrometer scale step sizes. Micrometer scale spacings of 2, 4 and 8 μm between fibronectin nanodots proved to modulate cell adhesion through modification of cell area, focal adhesion number, size and circularity. Overall, cell behavior was shown to shift at the apparent threshold of 4 μm spacing. The findings presented here offer exciting new opportunities for cell biology research.

Chemical modifications of renewable cellulosic materials

USDA-ARS?s Scientific Manuscript database

In agriculture, there is a fair amount of byproducts and waste materials. These materials typically contain significant portions of cellulose and hemicellulose. A good opportunity is to take advantage of these relatively cheap renewable materials, carry out chemical reactions, and increase their v...

48 CFR 52.215-21 - Requirements for Certified Cost or Pricing Data and Data Other Than Certified Cost or Pricing...

Code of Federal Regulations, 2010 CFR

2010-10-01

... modifications under this contract, for price adjustments expected to exceed the threshold set forth at FAR 15.403-4 on the date of the agreement on price or the date of the award, whichever is later, the... the extent necessary to determine whether an exception should be granted, and whether the price is...

Quantitative proteomic characterization of redox-dependent post-translational modifications on protein cysteines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duan, Jicheng; Gaffrey, Matthew J.; Qian, Wei-Jun

Protein cysteine thiols play a crucial role in redox signaling, regulation of enzymatic activity and protein function, and maintaining redox homeostasis in living systems. The unique chemical reactivity of thiol groups makes cysteine susceptible to oxidative modifications by reactive oxygen and nitrogen species to form a broad array of reversible and irreversible protein post-translational modifications (PTMs). The reversible modifications in particular are one of the major components of redox signaling and are involved in regulation of various cellular processes under physiological and pathological conditions. The biological significance of these redox PTMs in health and diseases has been increasingly recognized. Herein,more » we review the recent advances of quantitative proteomic approaches for investigating redox PTMs in complex biological systems, including the general considerations of sample processing, various chemical or affinity enrichment strategies, and quantitative approaches. We also highlight a number of redox proteomic approaches that enable effective profiling of redox PTMs for addressing specific biological questions. Although some technological limitations remain, redox proteomics is paving the way towards a better understanding of redox signaling and regulation in human health and diseases.« less

Incorporation of post-translational modified amino acids as an approach to increase both chemical and biological diversity of conotoxins and conopeptides.

PubMed

Espiritu, Michael J; Cabalteja, Chino C; Sugai, Christopher K; Bingham, Jon-Paul

2014-01-01

Bioactive peptides from Conus venom contain a natural abundance of post-translational modifications that affect their chemical diversity, structural stability, and neuroactive properties. These modifications have continually presented hurdles in their identification and characterization. Early endeavors in their analysis relied on classical biochemical techniques that have led to the progressive development and use of novel proteomic-based approaches. The critical importance of these post-translationally modified amino acids and their specific assignment cannot be understated, having impact on their folding, pharmacological selectivity, and potency. Such modifications at an amino acid level may also provide additional insight into the advancement of conopeptide drugs in the quest for precise pharmacological targeting. To achieve this end, a concerted effort between the classical and novel approaches is needed to completely elucidate the role of post-translational modifications in conopeptide structure and dynamics. This paper provides a reflection in the advancements observed in dealing with numerous and multiple post-translationally modified amino acids within conotoxins and conopeptides and provides a summary of the current techniques used in their identification.

On the Electrodeposition of Ca-P Coatings on Nitinol Alloy: A Comparison Between Different Surface Modification Methods

NASA Astrophysics Data System (ADS)

Etminanfar, M. R.; Khalil-Allafi, J.

2016-02-01

In this study, a combination of surface modification process and the electrochemical deposition of Ca-P coatings was used for the modification of the Nitinol shape memory alloy. DSC, SEM, GIB-XRD, FT-Raman, XPS, and FTIR measurements were performed for the characterization of the samples. Results indicated that chemical etching and boiling of the samples in distilled water formed TiO film on the surface. After the chemical modification, subsequent aging of the sample, at 470 °C for 30 min, converted the oxide film to a stable structure of titanium dioxide. In that case, the treated substrate indicated a superelastic behavior. At the same electrochemical condition, the treated substrate revealed more stable and uniform Ca-P coatings in comparison with the abraded Nitinol substrate. This difference was attributed to the presence of hydroxyl groups on the titanium dioxide surface. Also, after soaking the sample in SBF, the needle-like coating on the treated substrate was completely covered with the hydroxyapatite phase which shows a good bioactivity of the coating.

Role of low density lipoprotein in the activation of plasma lysolecithin acyltransferase activity. Effect of chemical and enzymatic modifications of the lipoprotein on enzyme activity.

PubMed

Subbaiah, P V; Chen, C H; Bagdade, J D; Albers, J J

1985-01-01

The effect of various chemical and enzymatic modifications of low density lipoprotein (LDL) on its ability to activate the isolated human plasma lysolecithin acyltransferase (LAT) was studied. Removal of all lipids from LDL resulted in the complete loss of LAT activation. Removal of only neutral lipids by extraction with heptane retained up to 50% of the original activity, which was not increased further by reconstitution of the LDL with the extracted lipids. Hydrolysis of the diacylphosphoglycerides of the LDL with phospholipases resulted in complete loss of LAT activation which was partially restored by the addition of egg lecithin. Hydrolysis of more than 4% of LDL protein by trypsin led to a linear decrease in activity with complete loss of activity occurring when about 25% of the LDL protein is hydrolyzed. Modification of the arginine groups of LDL reversibly inhibited the activation of LAT. Modification of lysine residues of LDL by acetylation, acetoacetylation or succinylation also abolished its ability to activate lysolecithin acylation.

Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

PubMed

Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

2013-11-01

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

Seizure susceptibility of neuropeptide-Y null mutant mice in amygdala kindling and chemical-induced seizure models.

PubMed

Shannon, Harlan E; Yang, Lijuan

2004-01-01

Neuropeptide Y (NPY) administered exogenously is anticonvulsant, and, NPY null mutant mice are more susceptible to kainate-induced seizures. In order to better understand the potential role of NPY in epileptogenesis, the present studies investigated the development of amygdala kindling, post-kindling seizure thresholds, and anticonvulsant effects of carbamazepine and levetiracetam in 129S6/SvEv NPY(+/+) and NPY(-/-) mice. In addition, susceptibility to pilocarpine- and kainate-induced seizures was compared in NPY(+/+) and (-/-) mice. The rate of amygdala kindling development did not differ in the NPY(-/-) and NPY(+/+) mice either when kindling stimuli were presented once daily for at least 20 days, or, 12 times daily for 2 days. However, during kindling development, the NPY(-/-) mice had higher seizure severity scores and longer afterdischarge durations than the NPY(+/+) mice. Post-kindling, the NPY(-/-) mice had markedly lower afterdischarge thresholds and longer afterdischarge durations than NPY (+/+) mice. Carbamazepine and levetiracetam increased the seizure thresholds of both NPY (-/-) and (+/+) mice. In addition, NPY (-/-) mice had lower thresholds for both kainate- and pilocarpine-induced seizures. The present results in amygdala kindling and chemical seizure models suggest that NPY may play a more prominent role in determining seizure thresholds and severity of seizures than in events leading to epileptogenesis. In addition, a lack of NPY does not appear to confer drug-resistance in that carbamazepine and levetiracetam were anticonvulsant in both wild type (WT) and NPY null mutant mice.

Late cataractogenesis caused by particulate radiations and photons in long-lived mammalian species

NASA Technical Reports Server (NTRS)

Lett, J. T.; Lee, A. C.; Cox, A. B.; Wood, D. H.

1989-01-01

Radiation cataractogenesis induced by small acute doses of particulate radiations and photons in the New Zealand white rabbit (Oryctolagus cuniculus), the beagle dog (Canis familiaris) and the rhesus monkey (Macaca mulatta) is discussed in the context of the use of animal models to assess the radiation hazards faced by humans during lengthy sojourns in deep space. Attention is paid to (1) the importance of lifespan studies with long-lived species - the above animals have median lifespans in captivity of 5-7, 13-14 and 25 years, respectively; and (2) the magnitudes of possible dose thresholds for cataractogenesis from sparsely ionizing radiations and the modifications of those thresholds by the late degenerative phase of the phenomenon.

Migraine, arousal and sleep deprivation: comment on: “sleep quality, arousal and pain thresholds in migraineurs: a blinded controlled polysomnographic study”

PubMed Central

2013-01-01

We discuss the hypothesis proposed by Engstrom and coworkers that Migraineurs have a relative sleep deprivation, which lowers the pain threshold and predispose to attacks. Previous data indicate that Migraineurs have a reduction of Cyclic Alternating Pattern (CAP), an essential mechanism of NREM sleep regulation which allows to dump the effect of incoming disruptive stimuli, and to protect sleep. The modifications of CAP observed in Migraineurs are similar to those observed in patients with impaired arousal (narcolepsy) and after sleep deprivation. The impairment of this mechanism makes Migraineurs more vulnerable to stimuli triggering attacks during sleep, and represents part of a more general vulnerability to incoming stimuli. PMID:23758606

Asymmetric band flipping for time-of-flight neutron diffraction data

DOE PAGES

Whitfield, Pamela S.; Coelho, Alan A.

2016-08-24

Charge flipping with powder diffraction data is known to produce a result more reliably with high-resolution data,i.e.visible reflections at smalldspacings. This data are readily accessible with the neutron time-of-flight technique but the assumption that negative scattering density is nonphysical is no longer valid where elements with negative scattering lengths are present. The concept of band flipping was introduced in the literature, where a negative threshold is used in addition to a positive threshold during the flipping. But, it was not tested with experimental data at the time. Finallly, band flipping has been implemented inTOPAStogether with the band modification of low-densitymore » elimination and tested with experimental powder and Laue single-crystal neutron data.« less

Study of the coalescence/splash threshold of droplet impact on liquid films and its relevance in assessing airborne particle release.

PubMed

Motzkus, C; Gensdarmes, F; Géhin, E

2011-10-15

Impingement of droplets on surfaces occurs in many industrial and natural processes. The study of droplet break-up is fundamental in order to determine the potential sources of airborne contamination for scenarios of hazardous liquid falls such as dripping. There are very few data in the literature describing the case of impact of millimetre-size droplets. The purposes of this work were to study experimentally particle emission during the impact of droplets on a liquid film and to assess the use of coalescence/splash relations to predict airborne particle release. The results are described using dimensionless numbers taking into account the inertial, viscosity and surface tension forces. Experiments were carried out for Weber numbers between 62 and 1754 and for Ohnesorge numbers between 2.0×10(-3) and 1.5×10(-2). New results on coalescence/splash thresholds are obtained using highly sensitive aerosol measurement and allow a prediction concerning the presence or absence of airborne particles according to a threshold relation. Moreover, we propose a modification of the Cossali et al.'s relation in order to describe the coalescence/prompt splash threshold. Copyright © 2011 Elsevier Inc. All rights reserved.

Chemical modification of coating of Pinus halepensis pollen by ozone exposure.

PubMed

Naas, Oumsaad; Mendez, Maxence; Quijada, Melesio; Gosselin, Sylvie; Farah, Jinane; Choukri, Ali; Visez, Nicolas

2016-07-01

Pollen coating, located on the exine, includes an extractible lipid fraction. The modification of the pollen coating by air pollutants may have implications on the interactions of pollen with plant stigmas and human cells. Pinus halepensis pollen was exposed to ozone in vitro and the pollen coating was extracted with organic solvent and analyzed by GC-MS. Ozone has induced chemical changes in the coating as observed with an increase in dicarboxylic acids, short-chain fatty acids and aldehydes. 4-Hydroxybenzaldehyde was identified as the main reaction product and its formation was shown to occur both on native pollen and on defatted pollen. 4-Hydroxybenzaldehyde is very likely formed via the ozonolysis of acid coumaric-like monomers constitutive of the sporopollenin. Modification of pollen coating by air pollutants should be accounted for in further studies on effect of pollution on germination and on allergenicity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Higher sensitivity secondary ion mass spectrometry of biological molecules for high resolution, chemically specific imaging.

PubMed

McDonnell, Liam A; Heeren, Ron M A; de Lange, Robert P J; Fletcher, Ian W

2006-09-01

To expand the role of high spatial resolution secondary ion mass spectrometry (SIMS) in biological studies, numerous developments have been reported in recent years for enhancing the molecular ion yield of high mass molecules. These include both surface modification, including matrix-enhanced SIMS and metal-assisted SIMS, and polyatomic primary ions. Using rat brain tissue sections and a bismuth primary ion gun able to produce atomic and polyatomic primary ions, we report here how the sensitivity enhancements provided by these developments are additive. Combined surface modification and polyatomic primary ions provided approximately 15.8 times more signal than using atomic primary ions on the raw sample, whereas surface modification and polyatomic primary ions yield approximately 3.8 and approximately 8.4 times more signal. This higher sensitivity is used to generate chemically specific images of higher mass biomolecules using a single molecular ion peak.

Multiphoton microscopy guides neurotrophin modification with poly(ethylene glycol) to enhance interstitial diffusion

NASA Astrophysics Data System (ADS)

Stroh, Mark; Zipfel, Warren R.; Williams, Rebecca M.; Ma, Shu Chin; Webb, Watt W.; Saltzman, W. Mark

2004-07-01

Brain-derived neurotrophic factor (BDNF) is a promising therapeutic agent for the treatment of neurodegenerative diseases. However, the limited distribution of this molecule after administration into the brain tissue considerably hampers its efficacy. Here, we show how multiphoton microscopy of fluorescently tagged BDNF in brain-tissue slices provides a useful and rapid screening method for examining the diffusion of large molecules in tissues, and for studying the effects of chemical modifications-for example, conjugating with polyethylene glycol (PEG)-on the diffusion constant. This single variable, obtained by monitoring short-term diffusion in real time, can be effectively used for rational drug design. In this study on fluorescently tagged BDNF and BDNF-PEG, we identify slow diffusion as a major contributing factor to the limited penetration of BDNF, and demonstrate how chemical modification can be used to overcome this barrier.

Cell signaling, post-translational protein modifications and NMR spectroscopy

PubMed Central

Theillet, Francois-Xavier; Smet-Nocca, Caroline; Liokatis, Stamatios; Thongwichian, Rossukon; Kosten, Jonas; Yoon, Mi-Kyung; Kriwacki, Richard W.; Landrieu, Isabelle; Lippens, Guy

2016-01-01

Post-translationally modified proteins make up the majority of the proteome and establish, to a large part, the impressive level of functional diversity in higher, multi-cellular organisms. Most eukaryotic post-translational protein modifications (PTMs) denote reversible, covalent additions of small chemical entities such as phosphate-, acyl-, alkyl- and glycosyl-groups onto selected subsets of modifiable amino acids. In turn, these modifications induce highly specific changes in the chemical environments of individual protein residues, which are readily detected by high-resolution NMR spectroscopy. In the following, we provide a concise compendium of NMR characteristics of the main types of eukaryotic PTMs: serine, threonine, tyrosine and histidine phosphorylation, lysine acetylation, lysine and arginine methylation, and serine, threonine O-glycosylation. We further delineate the previously uncharacterized NMR properties of lysine propionylation, butyrylation, succinylation, malonylation and crotonylation, which, altogether, define an initial reference frame for comprehensive PTM studies by high-resolution NMR spectroscopy. PMID:23011410

DOE Office of Scientific and Technical Information (OSTI.GOV)

Low, K.S.; Lee, C.K.; Lee, P.L.

The use of low-cost biological materials for the removal and recovery of heavy metals from solution has been investigated extensively in recent times. To enhance their sorption capacities various chemical modifications on the sorbents were attempted. Freer et al. showed that bark from the Pinus radiata (D. Don) had a greater sorption capacity for metals after treatment with both inorganic acid and formaldehyde. Apple wastes treated with phosphorus oxychloride improved the efficiency of removing metal ions. Ethylenediamine tetraacetic acid (EDTA)-modified groundnut, Arachis hypogea, was reported to improve the sorption of cadmium and lead ions. Modifications with the aid of dyesmore » also enhanced metal sorption. Moss and coconut husk (CH) are readily obtainable in Malaysia. Their sorption potential for metals has been reported. This paper reports on the metal sorption enhancement of these two biosorbents after chemical modification with nitrilotriacetic acid (NTA). 13 refs., 5 figs., 2 tabs.« less

Physical, Chemical and Biochemical Modifications of Protein-Based Films and Coatings: An Extensive Review

PubMed Central

Zink, Joël; Wyrobnik, Tom; Prinz, Tobias; Schmid, Markus

2016-01-01

Protein-based films and coatings are an interesting alternative to traditional petroleum-based materials. However, their mechanical and barrier properties need to be enhanced in order to match those of the latter. Physical, chemical, and biochemical methods can be used for this purpose. The aim of this article is to provide an overview of the effects of various treatments on whey, soy, and wheat gluten protein-based films and coatings. These three protein sources have been chosen since they are among the most abundantly used and are well described in the literature. Similar behavior might be expected for other protein sources. Most of the modifications are still not fully understood at a fundamental level, but all the methods discussed change the properties of the proteins and resulting products. Mastering these modifications is an important step towards the industrial implementation of protein-based films. PMID:27563881

Favorable 2'-substitution in the loop region of a thrombin-binding DNA aptamer.

PubMed

Awachat, Ragini; Wagh, Atish A; Aher, Manisha; Fernandes, Moneesha; Kumar, Vaijayanti A

2018-06-01

Simple 2'-OMe-chemical modification in the loop region of the 15mer G-rich DNA sequence GGTTGGTGTGGTTGG is reported. The G-quadruplex structure of this thrombin-binding aptamer (TBA), is stabilized by single modifications (T → 2'-OMe-U), depending on the position of the modification. The structural stability also renders significantly increased inhibition of thrombin-induced fibrin polymerization, a process closely associated with blood-clotting. Copyright © 2018 Elsevier Ltd. All rights reserved.

Changes in mechanical, chemical, and thermal sensitivity of the cornea after topical application of nonsteroidal anti-inflammatory drugs.

PubMed

Acosta, M Carmen; Berenguer-Ruiz, Leticia; García-Gálvez, Alberto; Perea-Tortosa, David; Gallar, Juana; Belmonte, Carlos

2005-01-01

In addition to their well-known anti-inflammatory actions, some of the nonsteroidal anti-inflammatory drugs (NSAIDs) appear to have an analgesic effect. In human subjects, the changes in threshold and intensity of sensations evoked by mechanical, chemical, and thermal stimulation of the cornea induced by topical administration of two commercial NSAIDs, diclofenac sodium (Voltaren; Novartis, Basel, Switzerland) and flurbiprofen (Ocuflur; Allergan, Irvine, CA), were studied. Corneal sensitivity was measured in 10 young, healthy subjects with a gas esthesiometer. Chemical (10%-70% CO2 in air), mechanical (0-264 mL/min), and thermal (corneal temperature changes between -4.5 degrees C and +3 degrees C around the normal value) stimuli were applied to the center of the cornea. The intensity and perceived magnitude of the psychophysical attributes of the evoked sensation were scored at the end of the pulse in a 10-cm, continuous visual analog scale (VAS). The threshold was expressed as the stimulus intensity that evoked a VAS score >0.5. Sensitivity was measured in both eyes of each subject on two separate days, one without treatment and the other 30 minutes after topical application of 0.03% flurbiprofen (seven subjects) or 0.1% diclofenac sodium (six subjects). Diclofenac attenuated significantly all the sensation parameters evoked by high-intensity mechanical, chemical, and thermal stimuli. Flurbiprofen produced a slight reduction of the sensations evoked by mechanical and chemical stimulation that became significant only for the irritation caused by chemical stimuli of maximum intensity (70% CO2). None of the drugs modified significantly the detection threshold of the different stimuli. Flurbiprofen had a very limited effect on sensations evoked by corneal stimulation, whereas diclofenac reduced the intensity of sensations evoked by stimuli of different modality, suggesting a mild local anesthetic effect of this drug on all types of corneal sensory fibers. Such anesthetic action could explain the analgesic effect that has been reported after topical application of diclofenac in inflamed human eyes.

GaN-based vertical-cavity surface-emitting lasers with tunnel junction contacts grown by metal-organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Lee, SeungGeun; Forman, Charles A.; Lee, Changmin; Kearns, Jared; Young, Erin C.; Leonard, John T.; Cohen, Daniel A.; Speck, James S.; Nakamura, Shuji; DenBaars, Steven P.

2018-06-01

We report the first demonstration of III–nitride vertical-cavity surface-emitting lasers (VCSELs) with tunnel junction (TJ) intracavity contacts grown completely by metal–organic chemical vapor deposition (MOCVD). For the TJs, n++-GaN was grown on in-situ activated p++-GaN after buffered HF surface treatment. The electrical properties and epitaxial morphologies of the TJs were first investigated on TJ LED test samples. A VCSEL with a TJ intracavity contact showed a lasing wavelength of 408 nm, a threshold current of ∼15 mA (10 kA/cm2), a threshold voltage of 7.8 V, a maximum output power of 319 µW, and a differential efficiency of 0.28%.

Rapid End-Group Modification of Polysaccharides for Biomaterial Applications in Regenerative Medicine.

PubMed

Bondalapati, Somasekhar; Ruvinov, Emil; Kryukov, Olga; Cohen, Smadar; Brik, Ashraf

2014-09-15

Polysaccharides have emerged as important functional materials because of their unique properties such as biocompatibility, biodegradability, and availability of reactive sites for chemical modifications to optimize their properties. The overwhelming majority of the methods to modify polysaccharides employ random chemical modifications, which often improve certain properties while compromising others. On the other hand, the employed methods for selective modifications often require excess of coupling partners, long reaction times and are limited in their scope and wide applicability. To circumvent these drawbacks, aniline-catalyzed oxime formation is developed for selective modification of a variety of polysaccharides through their reducing end. Notably, it is found that for efficient oxime formation, different conditions are required depending on the composition of the specific polysaccharide. It is also shown how our strategy can be applied to improve the physical and functional properties of alginate hydrogels, which are widely used in tissue engineering and regenerative medicine applications. While the randomly and selectively modified alginate exhibits similar viscoelastic properties, the latter forms significantly more stable hydrogel and superior cell adhesive and functional properties. Our results show that the developed conjugation reaction is robust and should open new opportunities for preparing polysaccharide-based functional materials with unique properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and physico-chemical characterization of modified starches from banana (Musa AAB) and its biological activities in diabetic rats.

PubMed

Reddy, Chagam Koteswara; Suriya, M; Vidya, P V; Haripriya, Sundaramoorthy

2017-01-01

This study describes a simple method of preparation and physico-chemical properties of modified starches (type-3 resistant starches) from banana (Musa AAB), and the modified starches investigated as functional food with a beneficial effect on type-2 diabetes. RS3 was prepared using a method combined with debranching modification and physical modification; native and modifies starches were characterized by scanning electron microscope (SEM), powder X-ray diffraction (XRD), differential scanning calorimetry (DSC) and rapid visco analyzer (RVA). Use of the enzymatic and physical modification methodology, improved the yield of RS (26.62%) from Musa AAB. A reduced viscosity and swelling power; increased transition temperatures, water absorption capacity and solubility index with B-type crystalline pattern and loss of granular appearance were observed during the debranching modification and physical modification. The modified starches exhibited beneficial health effects in diabetic and HFD rats who consumed it. These results recommend that dietary feeding of RS3 was effective in the regulation of glucose and lipid profile in serum and suppressing the oxidative stress in rats under diabetic and HFD condition. This current study provides new bioactive starches, with potential applications in the food and non-food industries. Copyright © 2016 Elsevier B.V. All rights reserved.

A tandem regression-outlier analysis of a ligand cellular system for key structural modifications around ligand binding.

PubMed

Lin, Ying-Ting

2013-04-30

A tandem technique of hard equipment is often used for the chemical analysis of a single cell to first isolate and then detect the wanted identities. The first part is the separation of wanted chemicals from the bulk of a cell; the second part is the actual detection of the important identities. To identify the key structural modifications around ligand binding, the present study aims to develop a counterpart of tandem technique for cheminformatics. A statistical regression and its outliers act as a computational technique for separation. A PPARγ (peroxisome proliferator-activated receptor gamma) agonist cellular system was subjected to such an investigation. Results show that this tandem regression-outlier analysis, or the prioritization of the context equations tagged with features of the outliers, is an effective regression technique of cheminformatics to detect key structural modifications, as well as their tendency of impact to ligand binding. The key structural modifications around ligand binding are effectively extracted or characterized out of cellular reactions. This is because molecular binding is the paramount factor in such ligand cellular system and key structural modifications around ligand binding are expected to create outliers. Therefore, such outliers can be captured by this tandem regression-outlier analysis.

Effects of carbon nanotube (CNT) dispersion and interface condition on thermo-mechanical behavior of CNT-reinforced vinyl ester

NASA Astrophysics Data System (ADS)

Sabet, Seyed Morteza

In fabrication of nanoparticle-reinforced polymers, two critical factors need to be taken into account to control properties of the final product; nanoparticle dispersion/distribution in the matrix; and interfacial interactions between nanoparticles and their surrounding matrix. The focus of this thesis was to examine the role of these two factors through experimental methodologies and molecular-level simulations. Carbon nanotubes (CNTs) and vinyl ester (VE) resin were used as nanoparticles and matrix, respectively. In a parametric study, a series of CNT/VE nanocomposites with different CNT dispersion conditions were fabricated using the ultrasonication mixing method. Thermomechanical properties of nanocomposites and quality of CNT dispersion were evaluated. By correlation between nanocomposite behavior and CNT dispersion, a thermomechanical model was suggested; at a certain threshold level of sonication energy, CNT dispersion would be optimal and result in maximum enhancement in properties. This threshold energy level is also related to particle concentration. Sonication above this threshold level, leads to destruction of nanotubes and renders a negative effect on the properties of nanocomposites. In an attempt to examine the interface condition, a novel process was developed to modify CNT surface with polyhedral oligomeric silsesquioxane (POSS). In this process, a chemical reaction was allowed to occur between CNTs and POSS in the presence of an effective catalyst. The functionalized CNTs were characterized using TEM, SEM-EDS, AFM, TGA, FTIR and Raman spectroscopy techniques. Formation of amide bonds between POSS and nanotubes was established and verified. Surface modification of CNTs with POSS resulted in significant improvement in nanotube dispersion. In-depth SEM analysis revealed formation of a 3D network of well-dispersed CNTs with POSS connections to the polymer. In parallel, molecular dynamics simulation of CNT-POSS/VE system showed an effective load transfer from polymer chains to the CNT due to POSS linkages at the interface. The rigid and flexible network of CNTs is found to be responsible for enhancement in elastic modulus, strength, fracture toughness and glass transition temperature (Tg) of the final nanocomposites.

A microfluidic flow-through device for high throughput electrical lysis of bacterial cells based on continuous dc voltage.

PubMed

Wang, Hsiang-Yu; Bhunia, Arun K; Lu, Chang

2006-12-15

Interest in electrical lysis of biological cells on a microfludic platform has increased because it allows for the rapid recovery of intracellular contents without introducing lytic agents. In this study we demonstrated a simple microfluidic flow-through device which lysed Escherichia coli cells under a continuous dc voltage. The E. coli cells had previously been modified to express green fluorescent protein (GFP). In our design, the cell lysis only happened in a defined section of a microfluidic channel due to the local field amplification by geometric modification. The geometric modification also effectively decreased the required voltage for lysis by several folds. We found that local field strength of 1000-1500 V/cm was required for nearly 100% cell death. This threshold field strength was considerably lower than the value reported in the literature, possibly due to the longer duration of the field [Lee, S.W., Tai, Y.C., 1999. Sens. Actuators A: Phys. 73, 74-79]. Cell lysis was detected by both plate count and fluorescence spectroscopy. The cell membrane was completely disintegrated in the lysis section of the microfluidic device, when the field strength was higher than 2000 V/cm. The devices were fabricated using low-cost soft lithography with channel widths considerably larger than the cell size to avoid clogging and ensure stable performance. Our tool will be ideal for high throughput processing of bacterial cells for chemical analysis of intracellular contents such as DNA and proteins. The application of continuous dc voltage greatly simplified the instrumentation compared to devices using electrical pulses for similar purposes. In principle, the same approach can also be applied for lysis of mammalian cells and electroporative transfection.

Chemical Methods for the Direct Detection and Labeling of S-Nitrosothiols

PubMed Central

Bechtold, Erika

2012-01-01

Abstract Significance: Posttranslational modification of proteins through phosphorylation, glycosylation, and oxidation adds complexity to the proteome by reversibly altering the structure and function of target proteins in a highly controlled fashion. Recent Advances: The study of reversible cysteine oxidation highlights a role for this oxidative modification in complex signal transduction pathways. Nitric oxide (NO), and its respective metabolites (including reactive nitrogen species), participates in a variety of these cellular redox processes, including the reversible oxidation of cysteine to S-nitrosothiols (RSNOs). RSNOs act as endogenous transporters of NO, but also possess beneficial effects independent of NO-related signaling, which suggests a complex and versatile biological role. In this review, we highlight the importance of RSNOs as a required posttranslational modification and summarize the current methods available for detecting S-nitrosation. Critical Issues: Given the limitations of these indirect detection methods, the review covers recent developments toward the direct detection of RSNOs by phosphine-based chemical probes. The intrinsic properties that dictate this phosphine/RSNO reactivity are summarized. In general, RSNOs (both small molecule and protein) react with phosphines to yield reactive S-substituted aza-ylides that undergo further reactions leading to stable RSNO-based adducts. Future Directions: This newly explored chemical reactivity forms the basis of a number of exciting potential chemical methods for protein RSNO detection in biological systems. Antioxid. Redox Signal. 17, 981–991. PMID:22356122

Utilization of magnetically responsive cereal by-product for organic dye removal.

PubMed

Baldikova, Eva; Politi, Dorothea; Maderova, Zdenka; Pospiskova, Kristyna; Sidiras, Dimitrios; Safarikova, Mirka; Safarik, Ivo

2016-04-01

Barley straw, an agricultural by-product, can also serve as a low-cost and relatively efficient adsorbent of various harmful compounds. In this case, adsorption of four water-soluble dyes belonging to different dye classes (specifically Bismarck brown Y, representing the azo group; methylene blue, quinone-imine group; safranin O, safranin group; and crystal violet, triphenylmethane group) on native and citric acid-NaOH-modified barley straw, both in magnetic and non-magnetic versions, was studied. The adsorption was characterized using three adsorption models, namely Langmuir, Freundlich and Sips. To compare the maximum adsorption capacities (qmax), the Langmuir model was employed. The qmax values reached 86.5-124.3 mg of dye per g of native non-magnetic straw and 410.8-520.3 mg of dye per g of magnetic chemically modified straw. Performed characterization studies suggested that the substantial increase in qmax values after chemical modification could be caused by rougher surface of adsorbent (observed by scanning electron microscopy) and by the presence of higher amounts of carboxyl groups (detected by Fourier transform infrared spectroscopy). The adsorption processes followed the pseudo-second-order kinetic model and thermodynamic studies indicated spontaneous and endothermic adsorption. The chemical modification of barley straw led to a significant increase in maximum adsorption capacities for all tested dyes, while magnetic modification substantially facilitated the manipulation with adsorbent. © 2015 Society of Chemical Industry.

Environmental chemical exposures and human epigenetics

PubMed Central

Hou, Lifang; Zhang, Xiao; Wang, Dong; Baccarelli, Andrea

2012-01-01

Every year more than 13 million deaths worldwide are due to environmental pollutants, and approximately 24% of diseases are caused by environmental exposures that might be averted through preventive measures. Rapidly growing evidence has linked environmental pollutants with epigenetic variations, including changes in DNA methylation, histone modifications and microRNAs. Environ mental chemicals and epigenetic changes All of these mechanisms are likely to play important roles in disease aetiology, and their modifications due to environmental pollutants might provide further understanding of disease aetiology, as well as biomarkers reflecting exposures to environmental pollutants and/or predicting the risk of future disease. We summarize the findings on epigenetic alterations related to environmental chemical exposures, and propose mechanisms of action by means of which the exposures may cause such epigenetic changes. We discuss opportunities, challenges and future directions for future epidemiology research in environmental epigenomics. Future investigations are needed to solve methodological and practical challenges, including uncertainties about stability over time of epigenomic changes induced by the environment, tissue specificity of epigenetic alterations, validation of laboratory methods, and adaptation of bioinformatic and biostatistical methods to high-throughput epigenomics. In addition, there are numerous reports of epigenetic modifications arising following exposure to environmental toxicants, but most have not been directly linked to disease endpoints. To complete our discussion, we also briefly summarize the diseases that have been linked to environmental chemicals-related epigenetic changes. PMID:22253299

Pipeline of Known Chemical Classes of Antibiotics

PubMed Central

d’Urso de Souza Mendes, Cristina; de Souza Antunes, Adelaide Maria

2013-01-01

Many approaches are used to discover new antibiotic compounds, one of the most widespread being the chemical modification of known antibiotics. This type of discovery has been so important in the development of new antibiotics that most antibiotics used today belong to the same chemical classes as antibiotics discovered in the 1950s and 1960s. Even though the discovery of new classes of antibiotics is urgently needed, the chemical modification of antibiotics in known classes is still widely used to discover new antibiotics, resulting in a great number of compounds in the discovery and clinical pipeline that belong to existing classes. In this scenario, the present article presents an overview of the R&D pipeline of new antibiotics in known classes of antibiotics, from discovery to clinical trial, in order to map out the technological trends in this type of antibiotic R&D, aiming to identify the chemical classes attracting most interest, their spectrum of activity, and the new subclasses under development. The result of the study shows that the new antibiotics in the pipeline belong to the following chemical classes: quinolones, aminoglycosides, macrolides, oxazolidinones, tetracyclines, pleuromutilins, beta-lactams, lipoglycopeptides, polymyxins and cyclic lipopeptides. PMID:27029317

[Multiple chemical sensitivity, a well-defined illness?].

PubMed

Kolstad, Henrik A; Silberschmidt, Martin; Nielsen, Jesper Bo; Osterberg, Kai; Andersen, Johan Hviid; Bonde, Jens Peter E; Fink, Per

2006-03-13

Some people react to smells or chemicals at levels far below toxicological thresholds with nonspecific symptoms, fear and social isolation. They may be diagnosed with multiple chemical sensitivity. There is no empirical evidence indicating that this condition is explained by toxicological mechanisms, even though a number of theories have been proposed. The authors of this review conclude that this is a functional condition. These patients need information and treatment in accordance with this fact. Instead of being advised how to avoid exposure to chemicals, they should be properly trained in appropriate confrontation with the chemicals encountered in everyday life.

Application of fuzzy c-means clustering to PRTR chemicals uncovering their release and toxicity characteristics.

PubMed

Xue, Mianqiang; Zhou, Liang; Kojima, Naoya; Dos Muchangos, Leticia Sarmento; Machimura, Takashi; Tokai, Akihiro

2018-05-01

Increasing manufacture and usage of chemicals have not been matched by the increase in our understanding of their risks. Pollutant release and transfer register (PRTR) is becoming a popular measure for collecting chemical data and enhancing the public right to know. However, these data are usually in high dimensionality which restricts their wider use. The present study partitions Japanese PRTR chemicals into five fuzzy clusters by fuzzy c-mean clustering (FCM) to explore the implicit information. Each chemical with membership degrees belongs to each cluster. Cluster I features high releases from non-listed industries and the household sector and high environmental toxicity. Cluster II is characterized by high reported releases and transfers from 24 listed industries above the threshold, mutagenicity, and high environmental toxicity. Chemicals in cluster III have characteristics of high releases from non-listed industries and low toxicity. Cluster IV is characterized by high reported releases and transfers from 24 listed industries above the threshold and extremely high environmental toxicity. Cluster V is characterized by low releases yet mutagenicity and high carcinogenicity. Chemicals with the highest membership degree were identified as representatives for each cluster. For the highest membership degree, half of the chemicals have a value higher than 0.74. If we look at both the highest and the second highest membership degrees simultaneously, about 94% of the chemicals have a value higher than 0.5. FCM can serve as an approach to uncover the implicit information of highly complex chemical dataset, which subsequently supports the strategy development for efficient and effective chemical management. Copyright © 2017 Elsevier B.V. All rights reserved.

The effect of exogenous GM1 ganglioside on kindled-amygdaloid seizures.

PubMed

Albertson, T E; Walby, W F

1987-01-01

The effects of 12 daily doses of 30 mg/kg GM1 ganglioside i.p. on the acquisition of kindled-amygdaloid seizures in the rat was studied. No modification in the rate of kindling or the expression of the elicited seizures was noted during the acquisition phase. Further studies with additional fully amygdaloid kindled rats failed to show significant modification of suprathreshold or threshold elicited seizures after single 30-60 mg/kg i.p. doses of GM1 ganglioside. Despite previous studies which have shown antibodies to GM1 ganglioside to be convulsive, no anticonvulsant activity was demonstrated in this study with exogenous GM1 ganglioside using a battery of kindled-amygdaloid seizure tests in the rat.

Nanocapillary Atmospheric Pressure Plasma Jet: A Tool for Ultrafine Maskless Surface Modification at Atmospheric Pressure.

PubMed

Motrescu, Iuliana; Nagatsu, Masaaki

2016-05-18

With respect to microsized surface functionalization techniques we proposed the use of a maskless, versatile, simple tool, represented by a nano- or microcapillary atmospheric pressure plasma jet for producing microsized controlled etching, chemical vapor deposition, and chemical modification patterns on polymeric surfaces. In this work we show the possibility of size-controlled surface amination, and we discuss it as a function of different processing parameters. Moreover, we prove the successful connection of labeled sugar chains on the functionalized microscale patterns, indicating the possibility to use ultrafine capillary atmospheric pressure plasma jets as versatile tools for biosensing, tissue engineering, and related biomedical applications.

Threshold detection of boar taint chemicals using parasitic wasps.

PubMed

Olson, Dawn; Wäckers, Felix; Haugen, John-Erik

2012-10-01

Surgical castration has been long used to prevent consumers from experiencing taint in meat from male pigs, which is a large problem in the pig husbandry industry. Due to obvious animal welfare issues, the EU now wants an alternative for castration, suggesting an urgent need for novel methods of boar taint detection. As boar taint is only a problem when taint chemicals exceed a well-defined threshold, detection methods should be concentration-specific. The wasp, Microplitis croceipes' ability to learn and respond to particular concentrations of the boar taint compounds, skatole, androstenone, and indole was tested. Also tested was the wasps' ability to discriminate between known concentrations of indole, skatole, and androstenone in real boar fat samples at room temperature. Wasps were trained using associative learning by providing food-deprived wasps with sucrose-water in the presence of specific odor concentrations. Trained wasps' responses were tested to a range of concentrations of 3 compounds. Wasps showed unidirectional generalization of learned concentration responses, whereby the direction of concentration generalization was shown to be chemical-dependent. Through both positive (sucrose) and negative feeding experiences (water only) with varying compound concentrations, the wasps can also be conditioned to respond to concentrations exceeding a defined threshold, and they were successful in reporting low, medium, and high concentrations of indole, skatole, and androstenone in boar fat at room temperature. The need for threshold detection rather than simple detection of absence/presence applies to many food quality issues, including the detection of spoilage or pest damage in crops or stored foods. An inexpensive and reliable means of detecting boar tainted pork at slaughter to avoid tainted meat on the market and dissatisfied consumers. Journal of Food Science © 2012 Institute of Food Technologists® No claim to original US government works.

Engineering specific chemical modification sites into a collagen-like protein from Streptococcus pyogenes.

PubMed

Stoichevska, Violet; Peng, Yong Y; Vashi, Aditya V; Werkmeister, Jerome A; Dumsday, Geoff J; Ramshaw, John A M

2017-03-01

Recombinant bacterial collagens provide a new opportunity for safe biomedical materials. They are readily expressed in Escherichia coli in good yield and can be readily purified by simple approaches. However, recombinant proteins are limited in that direct secondary modification during expression is generally not easily achieved. Thus, inclusion of unusual amino acids, cyclic peptides, sugars, lipids, and other complex functions generally needs to be achieved chemically after synthesis and extraction. In the present study, we have illustrated that bacterial collagens that have had their sequences modified to include cysteine residue(s), which are not normally present in bacterial collagen-like sequences, enable a range of specific chemical modification reactions to be produced. Various model reactions were shown to be effective for modifying the collagens. The ability to include alkyne (or azide) functions allows the extensive range of substitutions that are available via "click" chemistry to be accessed. When bifunctional reagents were used, some crosslinking occurred to give higher molecular weight polymeric proteins, but gels were not formed. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 806-813, 2017. © 2016 Wiley Periodicals, Inc.

Synthesis of inulin derivatives with quaternary phosphonium salts and their antifungal activity.

PubMed

Chen, Yuan; Tan, Wenqiang; Li, Qing; Dong, Fang; Gu, Guodong; Guo, Zhanyong

2018-07-01

Inulin is a kind of renewable and biodegradable carbohydrate with good water solubility and numerous physiological functions. For further utilization of inulin, chemical modification can be applied to improve its bioactivities. In this paper, five novel inulin derivatives were synthesized via chemical modification with quaternary phosphonium salt. Their antifungal activity against three kinds of plant pathogens including Colletotrichum lagenarium, Phomopsis asparagi, and Fusarium oxysporum was assessed with radial growth assay in vitro. Results revealed that all the inulin derivatives exhibited improved antifungal activity compared with inulin. Particularly, inulin modified with triphenylphosphine (TPhPAIL) exhibited the best antifungal activity with inhibitory indices of 80.0%, 78.8%, and 87.4% against Colletotrichum lagenarium, Phomopsis asparagi, and Fusarium oxysporum at 1.0mg/mL respectively. The results clearly showed that chemical modification of inulin with quaternary phosphonium salt could efficiently improve derivatives' antifungal activity. Further analysis of results indicated that the antifungal activity was influenced by alkyl chain length or electron-withdrawing ability of the grafted quaternary phosphonium salts. Longer alkyl chain lengths or the stronger electron-withdrawing groups would lead to enhanced antifungal efficacy. Copyright © 2018 Elsevier B.V. All rights reserved.

Mass Spectrometry of Intact Proteins Reveals +98 u Chemical Artifacts Following Precipitation in Acetone.

PubMed

Güray, Melda Z; Zheng, Shi; Doucette, Alan A

2017-02-03

Protein precipitation in acetone is frequently employed ahead of mass spectrometry for sample preconcentration and purification. Unfortunately, acetone is not chemically inert; mass artifacts have previously been observed on glycine-containing peptides when exposed to acetone under acidic conditions. We herein report a distinct chemical modification occurring at the level of intact proteins when incubated in acetone. This artifact manifests as one or more satellite peaks in the MS spectrum of intact protein, spaced 98 u above the mass of the unmodified protein. Other artifacts (+84, +112 u) also appear upon incubation of proteins or peptides in acetone. The reaction is pH-sensitive, being suppressed when proteins are exposed to acetone under acidic conditions. The +98 u artifact is speculated to originate through an intermediate product of aldol condensation of acetone to form diacetone alcohol and mesityl oxide. A +98 u product could originate from nucleophilic attack on mesityl oxide or through condensation with diacetone alcohol. Given the extent of modification possible upon exposure of proteins to acetone, particularly following overnight solvent exposure or incubation at room temperature, an awareness of the variables influencing this novel modification is valued by proteomics researchers who employ acetone precipitation for protein purification.

Secondary structure model of the RNA recognized by the reverse transcriptase from the R2 retrotransposable element.

PubMed Central

Mathews, D H; Banerjee, A R; Luan, D D; Eickbush, T H; Turner, D H

1997-01-01

RNA transcripts corresponding to the 250-nt 3' untranslated region of the R2 non-LTR retrotransposable element are recognized by the R2 reverse transcriptase and are sufficient to serve as templates in the target DNA-primed reverse transcription (TPRT) reaction. The R2 protein encoded by the Bombyx mori R2 can recognize this region from both the B. mori and Drosophila melanogaster R2 elements even though these regions show little nucleotide sequence identity. A model for the RNA secondary structure of the 3' untranslated region of the D. melanogaster R2 retrotransposon was developed by sequence comparison of 10 species aided by free energy minimization. Chemical modification experiments are consistent with this prediction. A secondary structure model for the 3' untranslated region of R2 RNA from the R2 element from B. mori was obtained by a combination of chemical modification data and free energy minimization. These two secondary structure models, found independently, share several common sites. This study shows the utility of combining free energy minimization, sequence comparison, and chemical modification to model an RNA secondary structure. PMID:8990394

Chemical modification of Saccharomycopsis fibuligera R64 α-amylase to improve its stability against thermal, chelator, and proteolytic inactivation.

PubMed

Ismaya, Wangsa Tirta; Hasan, Khomaini; Kardi, Idar; Zainuri, Amalia; Rahmawaty, Rinrin Irma; Permanahadi, Satyawisnu; El Viera, Baiq Vera; Harinanto, Gunawan; Gaffar, Shabarni; Natalia, Dessy; Subroto, Toto; Soemitro, Soetijoso

2013-05-01

α-Amylase catalyzes hydrolysis of starch to oligosaccharides, which are further degraded to simple sugars. The enzyme has been widely used in food and textile industries and recently, in generation of renewable energy. An α-amylase from yeast Saccharomycopsis fibuligera R64 (Sfamy) is active at 50 °C and capable of degrading raw starch, making it attractive for the aforementioned applications. To improve its characteristics as well as to provide information for structural study ab initio, the enzyme was chemically modified by acid anhydrides (nonpolar groups), glyoxylic acid (GA) (polar group), dimethyl adipimidate (DMA) (cross-linking), and polyethylene glycol (PEG) (hydrophilization). Introduction of nonpolar groups increased enzyme stability up to 18 times, while modification by a cross-linking agent resulted in protection of the calcium ion, which is essential for enzyme activity and integrity. The hydrophilization with PEG resulted in protection against tryptic digestion. The chemical modification of Sfamy by various modifiers has thereby resulted in improvement of its characteristics and provided systematic information beneficial for structural study of the enzyme. An in silico structural study of the enzyme improved the interpretation of the results.

Therapeutic charm of quercetin and its derivatives: a review of research and patents.

PubMed

Sharma, Ajay; Kashyap, Dharambir; Sak, Katrin; Tuli, Hardeep Singh; Sharma, Anil K

2018-01-01

Bioactive polyphenolic compounds derived from plants are being utilized for prevention of various chronic diseases including cancer and cardiovascular disorders. Quercetin, a potential poly-phenolic flavonol, found in onions, apples and berries, has been implicated against cancer proliferation, chronic inflammation and various other oxidative manifestations. Evidences suggested that quercetin negatively regulates the numerous crucial signaling pathways associated with life-threatening diseases. Major signaling pathways including NF-κB, MAPK, PI3K-AKT and mTOR are found to be regulated by quercetin. In addition, several patents have reported recently on quercetin derivatives describing wide therapeutic applications such as anticancer/antiproliferatory, antioxidative/antiaging, antiviral, anti-inflammatory, cardioprotective. Present review emphasizes the chemistry and sources of quercetin followed by description of its broad-spectrum therapeutic potential along with proposed mechanisms of action. Furthermore, this review also highlights the important modifications in the basic chemical structure of quercetin in terms of published patents. Insolubility of the bioactive compounds restricts their medicinal importance which could be overcome by modifications in the chemical structure of so-called derivatives. Most of the patents deal with the modifications in chemical structure of quercetin mainly at hydroxyl groups and C-6 and C-7 positions.

78 FR 65570 - Modification of Significant New Uses of 1-Propene, 2,3,3,3-tetrafluoro-

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-01

... include, but are not limited to: Manufacturers or processors of the subject chemical substance (NAICS... by this action. Other types of entities not listed in this unit could also be affected. The North... modification. One of the commenters also noted a potential ambiguity in the proposed regulatory text. Part of...

Ring structure modifications of phenylalanine 19 increase fibrillation kinetics and reduce toxicity of amyloid β (1-40).

PubMed

Korn, Alexander; Surendran, Dayana; Krueger, Martin; Maiti, Sudipta; Huster, Daniel

2018-05-24

We investigated the influence of the chemical structure of the phenylalanine side chain in position 19 of the 40 residue amyloid β peptide. Side chain modifications in this position yielded fibrils of essentially unaltered morphology, structure, and dynamics, but significantly increased fibrillation kinetics and diminished the toxicity of the peptides.

Structural and physico-chemical properties of insoluble rice bran fiber: effect of acid–base induced modifications

USDA-ARS?s Scientific Manuscript database

The structural modifications of insoluble rice bran fiber (IRBF) by sequential regimes of sulphuric acid (H2SO4) and their effects on the physicochemical attributes were studied. The increment of H2SO4 concentration resulted in decreased water holding capacity that ultimately enhanced the oil bindin...

RNA methylation in nuclear pre-mRNA processing.

PubMed

Covelo-Molares, Helena; Bartosovic, Marek; Vanacova, Stepanka

2018-06-19

Eukaryotic RNA can carry more than 100 different types of chemical modifications. Early studies have been focused on modifications of highly abundant RNA, such as ribosomal RNA and transfer RNA, but recent technical advances have made it possible to also study messenger RNA (mRNA). Subsequently, mRNA modifications, namely methylation, have emerged as key players in eukaryotic gene expression regulation. The most abundant and widely studied internal mRNA modification is N 6 -methyladenosine (m 6 A), but the list of mRNA chemical modifications continues to grow as fast as interest in this field. Over the past decade, transcriptome-wide studies combined with advanced biochemistry and the discovery of methylation writers, readers, and erasers revealed roles for mRNA methylation in the regulation of nearly every aspect of the mRNA life cycle and in diverse cellular, developmental, and disease processes. Although large parts of mRNA function are linked to its cytoplasmic stability and regulation of its translation, a number of studies have begun to provide evidence for methylation-regulated nuclear processes. In this review, we summarize the recent advances in RNA methylation research and highlight how these new findings have contributed to our understanding of methylation-dependent RNA processing in the nucleus. This article is categorized under: RNA Processing > RNA Editing and Modification RNA Processing > Splicing Regulation/Alternative Splicing RNA Interactions with Proteins and Other Molecules > Protein-RNA Interactions: Functional Implications. © 2018 The Authors. WIREs RNA published by Wiley Periodicals, Inc.

Comparative Study of Surface Chemical Composition and Oxide Layer Modification upon Oxygen Plasma Cleaning and Piranha Etching on a Novel Low Elastic Modulus Ti25Nb21Hf Alloy

NASA Astrophysics Data System (ADS)

Paredes, Virginia; Salvagni, Emiliano; Rodríguez-Castellón, Enrique; Manero, José María

2017-08-01

Metals are widely employed for many biological artificial replacements, and it is known that the quality and the physical/chemical properties of the surface are crucial for the success of the implant. Therefore, control over surface implant materials and their elastic moduli may be crucial to avoid undesired effects. In this study, surface modification upon cleaning and activation of a low elastic modulus Ti alloy (Ti25Hf21Nb) was investigated. Two different methods, oxygen plasma (OP) cleaning and piranha (PI) solution, were studied and compared. Both surface treatments were effective for organic contaminant removal and to increase the Ti-oxide layer thickness rather than other metal-oxides present at the surface, which is beneficial for biocompatibility of the material. Furthermore, both techniques drastically increased hydrophilicity and introduced oxidation and hydroxylation (OH)-functional groups at the surface that may be beneficial for further chemical modifications. However, these treatments did not alter the surface roughness and bulk material properties. The surfaces were fully characterized in terms of surface roughness, wettability, oxide layer composition, and hydroxyl surface density through analytical techniques (interferometry, X-ray photoelectron spectroscopy (XPS), contact angle, and zinc complexation). These findings provide essential information when planning surface modifications for cleanliness, oxide layer thickness, and surface hydroxyl density, as control over these factors is essential for many applications, especially in biomaterials.

Intensity and absorbed-power distribution in a cylindrical solar-pumped dye laser

NASA Technical Reports Server (NTRS)

Williams, M. D.

1984-01-01

The internal intensity and absorbed-power distribution of a simplified hypothetical dye laser of cylindrical geometry is calculated. Total absorbed power is also calculated and compared with laboratory measurements of lasing-threshold energy deposition in a dye cell to determine the suitability of solar radiation as a pump source or, alternatively, what modifications, if any, are necessary to the hypothetical system for solar pumping.

Energy deposition by heavy ions: Additivity of kinetic and potential energy contributions in hillock formation on CaF2

PubMed Central

Wang, Y. Y.; Grygiel, C.; Dufour, C.; Sun, J. R.; Wang, Z. G.; Zhao, Y. T.; Xiao, G. Q.; Cheng, R.; Zhou, X. M.; Ren, J. R.; Liu, S. D.; Lei, Y.; Sun, Y. B.; Ritter, R.; Gruber, E.; Cassimi, A.; Monnet, I.; Bouffard, S.; Aumayr, F.; Toulemonde, M.

2014-01-01

Modification of surface and bulk properties of solids by irradiation with ion beams is a widely used technique with many applications in material science. In this study, we show that nano-hillocks on CaF2 crystal surfaces can be formed by individual impact of medium energy (3 and 5 MeV) highly charged ions (Xe22+ to Xe30+) as well as swift (kinetic energies between 12 and 58 MeV) heavy xenon ions. For very slow highly charged ions the appearance of hillocks is known to be linked to a threshold in potential energy (Ep) while for swift heavy ions a minimum electronic energy loss per unit length (Se) is necessary. With our results we bridge the gap between these two extreme cases and demonstrate, that with increasing energy deposition via Se the Ep-threshold for hillock production can be lowered substantially. Surprisingly, both mechanisms of energy deposition in the target surface seem to contribute in an additive way, which can be visualized in a phase diagram. We show that the inelastic thermal spike model, originally developed to describe such material modifications for swift heavy ions, can be extended to the case where both kinetic and potential energies are deposited into the surface. PMID:25034006

Energy deposition by heavy ions: additivity of kinetic and potential energy contributions in hillock formation on CaF2.

PubMed

Wang, Y Y; Grygiel, C; Dufour, C; Sun, J R; Wang, Z G; Zhao, Y T; Xiao, G Q; Cheng, R; Zhou, X M; Ren, J R; Liu, S D; Lei, Y; Sun, Y B; Ritter, R; Gruber, E; Cassimi, A; Monnet, I; Bouffard, S; Aumayr, F; Toulemonde, M

2014-07-18

Modification of surface and bulk properties of solids by irradiation with ion beams is a widely used technique with many applications in material science. In this study, we show that nano-hillocks on CaF2 crystal surfaces can be formed by individual impact of medium energy (3 and 5 MeV) highly charged ions (Xe(22+) to Xe(30+)) as well as swift (kinetic energies between 12 and 58 MeV) heavy xenon ions. For very slow highly charged ions the appearance of hillocks is known to be linked to a threshold in potential energy (Ep) while for swift heavy ions a minimum electronic energy loss per unit length (Se) is necessary. With our results we bridge the gap between these two extreme cases and demonstrate, that with increasing energy deposition via Se the Ep-threshold for hillock production can be lowered substantially. Surprisingly, both mechanisms of energy deposition in the target surface seem to contribute in an additive way, which can be visualized in a phase diagram. We show that the inelastic thermal spike model, originally developed to describe such material modifications for swift heavy ions, can be extended to the case where both kinetic and potential energies are deposited into the surface.

Changing mothers' perception of infant emotion: a pilot study.

PubMed

Carnegie, Rebecca; Shepherd, C; Pearson, R M; Button, K S; Munafò, M R; Evans, J; Penton-Voak, I S

2016-02-01

Cognitive bias modification (CBM) techniques, which experimentally retrain abnormal processing of affective stimuli, are becoming established for various psychiatric disorders. Such techniques have not yet been applied to maternal processing of infant emotion, which is affected by various psychiatric disorders. In a pilot study, mothers of children under 3 years old (n =  2) were recruited and randomly allocated to one of three training exercises, aiming either to increase or decrease their threshold of perceiving distress in a morphed continuum of 15 infant facial images. Differences between pre- and post-training threshold were analysed between and within subjects. Compared to baseline thresholds, the threshold for perceiving infant distress decreased in the lowered threshold group (mean difference -1.7 frames, 95 % confidence intervals (CI) -3.1 to -0.3, p = 0.02), increased in the raised threshold group (1.3 frames, 95 % CI 0.6 to 2.1, p < 0.01) and was unchanged in the control group (0.1 frames, 95 % CI -0.8 to 1.1, p = 0.80). Between-group differences were similarly robust in regression models and were not attenuated by potential confounders. The findings suggest that it is possible to change the threshold at which mothers perceive ambiguous infant faces as distressed, either to increase or decrease sensitivity to distress. This small study was intended to provide proof of concept (i.e. that it is possible to alter a mother's perception of infant distress). Questions remain as to whether the effects persist beyond the immediate experimental session, have an impact on maternal behaviour and could be used in clinical samples to improve maternal sensitivity and child outcomes.

Student’s mental model, misconceptions, troublesome knowledge, and threshold concept on thermochemistry with DToM-POE

NASA Astrophysics Data System (ADS)

Wiji, W.; Mulyani, S.

2018-05-01

The purpose of this study is to obtain a profile of students' mental models, misconceptions, troublesome knowledge, and threshold concept on thermochemistry. The subjects in this study were 35 students. The method used in this research was descriptive method with instruments Diagnostic Test of Mental Model - Prediction, Observation, and Explanation (DToM-POE). The results showed that the students' ability to predict, observe, and explain ΔH of neutralization reaction of NaOH with HCl was still lacking. Most students tended to memorize chemical concepts related to symbolic level and they did not understand the meaning of the symbols used. Furthermore, most students were unable to connect the results of observations at the macroscopic level with the symbolic level to determine ΔH of neutralization reaction of NaOH with HCl. Then, most students tended to give an explanation by a net ionic equation or a chemical reaction equation at the symbolic level when explaining ΔH of neutralization reaction at the submicroscopic level. In addition, there are seven misconceptions, three troublesome knowledges, and three threshold concepts held by students on thermochemistry.

Biphasic responses in multi-site phosphorylation systems.

PubMed

Suwanmajo, Thapanar; Krishnan, J

2013-12-06

Multi-site phosphorylation systems are repeatedly encountered in cellular biology and multi-site modification is a basic building block of post-translational modification. In this paper, we demonstrate how distributive multi-site modification mechanisms by a single kinase/phosphatase pair can lead to biphasic/partial biphasic dose-response characteristics for the maximally phosphorylated substrate at steady state. We use simulations and analysis to uncover a hidden competing effect which is responsible for this and analyse how it may be accentuated. We build on this to analyse different variants of multi-site phosphorylation mechanisms showing that some mechanisms are intrinsically not capable of displaying this behaviour. This provides both a consolidated understanding of how and under what conditions biphasic responses are obtained in multi-site phosphorylation and a basis for discriminating between different mechanisms based on this. We also demonstrate how this behaviour may be combined with other behaviour such as threshold and bistable responses, demonstrating the capacity of multi-site phosphorylation systems to act as complex molecular signal processors.

Chemical modification of corn fiber with ion-exchanging groups

USDA-ARS?s Scientific Manuscript database

Pretreated corn fiber was chemically modified with quaternary ammonium group or/and sulfonated with 3-chloro-2-hydroxypropanesulfonic acid under vacuum or at ambient pressure. The soluble fraction was dialyzed through 1 kDa MWCO dialysis tubing and the material retained inside the tubing was filtere...

High-Pressure CO2 Sorption in Polymers of Intrinsic Microporosity under Ultrathin Film Confinement.

PubMed

Ogieglo, Wojciech; Ghanem, Bader; Ma, Xiaohua; Wessling, Matthias; Pinnau, Ingo

2018-04-04

Ultrathin microporous polymer films are pertinent to the development and further spread of nanotechnology with very promising potential applications in molecular separations, sensors, catalysis, or batteries. Here, we report high-pressure CO 2 sorption in ultrathin films of several chemically different polymers of intrinsic microporosity (PIMs), including the prototypical PIM-1. Films with thicknesses down to 7 nm were studied using interference-enhanced in situ spectroscopic ellipsometry. It was found that all PIMs swell much more than non-microporous polystyrene and other high-performance glassy polymers reported previously. Furthermore, chemical modifications of the parent PIM-1 strongly affected the swelling magnitude. By investigating the behavior of relative refractive index, n rel , it was possible to study the interplay between micropores filling and matrix expansion. Remarkably, all studied PIMs showed a maximum in n rel at swelling of 2-2.5% indicating a threshold point above which the dissolution in the dense matrix started to dominate over sorption in the micropores. At pressures above 25 bar, all PIMs significantly plasticized in compressed CO 2 and for the ones with the highest affinity to the penetrant, a liquidlike mixing typical for rubbery polymers was observed. Reduction of film thickness below 100 nm revealed pronounced nanoconfinement effects and resulted in a large swelling enhancement and a quick loss of the ultrarigid character. On the basis of the partial molar volumes of the dissolved CO 2 , the effective reduction of the T g was estimated to be ∼200 °C going from 128 to 7 nm films.

Net Reaction Rate and Neutrino Cooling Rate for the Urca Process in Departure from Chemical Equilibrium in the Crust of Fast-accreting Neutron Stars

NASA Astrophysics Data System (ADS)

Wang, Wei-Hua; Huang, Xi; Zheng, Xiao-Ping

We discuss the effect of compression on Urca shells in the ocean and crust of accreting neutron stars, especially in superbursting sources. We find that Urca shells may be deviated from chemical equilibrium in neutron stars which accrete at several tenths of the local Eddington accretion rate. The deviation depends on the energy threshold of the parent and daughter nuclei, the transition strength, the temperature, and the local accretion rate. In a typical crust model of accreting neutron stars, the chemical departures range from a few tenths of kBT to tens of kBT for various Urca pairs. If the Urca shell can exist in crusts of accreting neutron stars, compression may enhance the net neutrino cooling rate by a factor of about 1-2 relative to the neutrino emissivity in chemical equilibrium. For some cases, such as Urca pairs with small energy thresholds and/or weak transition strength, the large chemical departure may result in net heating rather than cooling, although the released heat can be small. Strong Urca pairs in the deep crust are hard to be deviated even in neutron stars accreting at the local Eddington accretion rate.

tRNAmodpred: a computational method for predicting posttranscriptional modifications in tRNAs

PubMed Central

Machnicka, Magdalena A.; Dunin-Horkawicz, Stanislaw; de Crécy-Lagard, Valerie; Bujnicki, Janusz M.

2016-01-01

tRNA molecules contain numerous chemically altered nucleosides, which are formed by enzymatic modification of the primary transcripts during the complex tRNA maturation process. Some of the modifications are introduced by single reactions, while other require complex series of reactions carried out by several different enzymes. The location and distribution of various types of modifications vary greatly between different tRNA molecules, organisms and organelles. We have developed a computational method tRNAmodpred, for predicting modifications in tRNA sequences. Briefly, our method takes as an input one or more unmodified tRNA sequences and a set of protein sequences corresponding to a proteome of a cell. Subsequently it identifies homologs of known tRNA modification enzymes in the proteome, predicts tRNA modification activities and maps them onto known pathways of RNA modification from the MODOMICS database. Thereby, theoretically possible modification pathways are identified, and products of these modification reactions are proposed for query tRNAs. This method allows for predicting modification patterns for newly sequenced genomes as well as for checking tentative modification status of tRNAs from one species treated with enzymes from another source, e.g. to predict the possible modifications of eukaryotic tRNAs expressed in bacteria. tRNAmodpred is freely available as web server at http://genesilico.pl/trnamodpred/. PMID:27016142

Hardware Modifications to the US Army Research Laboratory’s Metalorganic Chemical Vapor Deposition (MOCVD) System for Optimization of Complex Oxide Thin Film Fabrication

DTIC Science & Technology

2015-04-01

studies on flow and thermal fields in MOCVD reactor. Chinese Science Bulletin. 2010;55:560–566. 36. Hampdensmith MJ, Kodas TT. Chemical vapor...Chemistry. 1995;19727–750. 47. Xu CY, Hampdensmith MJ, Kodas TT. Aerosol-assisted chemical-vapor- deposition (AACVD) of binary alloy (AGXPD1-X, CUXPD1-X

The effect on biological and moisture resistance of epichlorohydrin chemically modified wood

Treesearch

Rebecca E. Ibach; Beom-Goo Lee

2002-01-01

Southern pine solid wood and fiber were chemically modified with epichlorohydrin to help in understanding the role of moisture in the mechanism of biological effectiveness of chemically modified wood. The solid wood had weight gains from 11% to 34%, while the fiber had weight gains from 9% to 75%. After modification, part of the specimens were water leached for 2 weeks...

The impact of climate change on ozone-related mortality in Sydney.

PubMed

Physick, William; Cope, Martin; Lee, Sunhee

2014-01-13

Coupled global, regional and chemical transport models are now being used with relative-risk functions to determine the impact of climate change on human health. Studies have been carried out for global and regional scales, and in our paper we examine the impact of climate change on ozone-related mortality at the local scale across an urban metropolis (Sydney, Australia). Using three coupled models, with a grid spacing of 3 km for the chemical transport model (CTM), and a mortality relative risk function of 1.0006 per 1 ppb increase in daily maximum 1-hour ozone concentration, we evaluated the change in ozone concentrations and mortality between decades 1996-2005 and 2051-2060. The global model was run with the A2 emissions scenario. As there is currently uncertainty regarding a threshold concentration below which ozone does not impact on mortality, we calculated mortality estimates for the three daily maximum 1-hr ozone concentration thresholds of 0, 25 and 40 ppb. The mortality increase for 2051-2060 ranges from 2.3% for a 0 ppb threshold to 27.3% for a 40 ppb threshold, although the numerical increases differ little. Our modeling approach is able to identify the variation in ozone-related mortality changes at a suburban scale, estimating that climate change could lead to an additional 55 to 65 deaths across Sydney in the decade 2051-2060. Interestingly, the largest increases do not correspond spatially to the largest ozone increases or the densest population centres. The distribution pattern of changes does not seem to vary with threshold value, while the magnitude only varies slightly.

Threshold-Voltage Shifts in Organic Transistors Due to Self-Assembled Monolayers at the Dielectric: Evidence for Electronic Coupling and Dipolar Effects.

PubMed

Aghamohammadi, Mahdieh; Rödel, Reinhold; Zschieschang, Ute; Ocal, Carmen; Boschker, Hans; Weitz, R Thomas; Barrena, Esther; Klauk, Hagen

2015-10-21

The mechanisms behind the threshold-voltage shift in organic transistors due to functionalizing of the gate dielectric with self-assembled monolayers (SAMs) are still under debate. We address the mechanisms by which SAMs determine the threshold voltage, by analyzing whether the threshold voltage depends on the gate-dielectric capacitance. We have investigated transistors based on five oxide thicknesses and two SAMs with rather diverse chemical properties, using the benchmark organic semiconductor dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene. Unlike several previous studies, we have found that the dependence of the threshold voltage on the gate-dielectric capacitance is completely different for the two SAMs. In transistors with an alkyl SAM, the threshold voltage does not depend on the gate-dielectric capacitance and is determined mainly by the dipolar character of the SAM, whereas in transistors with a fluoroalkyl SAM the threshold voltages exhibit a linear dependence on the inverse of the gate-dielectric capacitance. Kelvin probe force microscopy measurements indicate this behavior is attributed to an electronic coupling between the fluoroalkyl SAM and the organic semiconductor.

Impact of cross-field motion on ablation of high-Z dust in fusion edge plasmas

DOE PAGES

Smirnov, R. D.; Krasheninnikov, S. I.

2017-07-05

The impact of cross-field motion of high-Z dust grains on their shielding by ablation cloud in edge plasmas of tokamaks is analyzed. The modification of the existing high-Z dust shielding theory is developed, which takes the dust motion effects into account. We show that the cross-field motion can lead to a large factor increase of the dust ablation rate, as compared to the previous model. It is also shown that the motion effects take place when the dust cross-field velocity exceeds a threshold value. We also obtain the dependencies of the dust ablation flux on the dust velocity and ofmore » the threshold velocity on the dust size and the ambient plasma temperature.« less

Impact of cross-field motion on ablation of high-Z dust in fusion edge plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smirnov, R. D.; Krasheninnikov, S. I.

The impact of cross-field motion of high-Z dust grains on their shielding by ablation cloud in edge plasmas of tokamaks is analyzed. The modification of the existing high-Z dust shielding theory is developed, which takes the dust motion effects into account. We show that the cross-field motion can lead to a large factor increase of the dust ablation rate, as compared to the previous model. It is also shown that the motion effects take place when the dust cross-field velocity exceeds a threshold value. We also obtain the dependencies of the dust ablation flux on the dust velocity and ofmore » the threshold velocity on the dust size and the ambient plasma temperature.« less

Permanent fine tuning of silicon microring devices by femtosecond laser surface amorphization and ablation.

PubMed

Bachman, Daniel; Chen, Zhijiang; Fedosejevs, Robert; Tsui, Ying Y; Van, Vien

2013-05-06

We demonstrate the fine tuning capability of femtosecond laser surface modification as a permanent trimming mechanism for silicon photonic components. Silicon microring resonators with a 15 µm radius were irradiated with single 400 nm wavelength laser pulses at varying fluences. Below the laser ablation threshold, surface amorphization of the crystalline silicon waveguides yielded a tuning rate of 20 ± 2 nm/J · cm(-2)with a minimum resonance wavelength shift of 0.10nm. Above that threshold, ablation yielded a minimum resonance shift of -1.7 nm. There was some increase in waveguide loss for both trimming mechanisms. We also demonstrated the application of the method by using it to permanently correct the resonance mismatch of a second-order microring filter.

Fatal Exertional Heat Stroke and American Football Players: The Need for Regional Heat-Safety Guidelines.

PubMed

Grundstein, Andrew J; Hosokawa, Yuri; Casa, Douglas J

2018-01-01

  Weather-based activity modification in athletics is an important way to minimize heat illnesses. However, many commonly used heat-safety guidelines include a uniform set of heat-stress thresholds that do not account for geographic differences in acclimatization.   To determine if heat-related fatalities among American football players occurred on days with unusually stressful weather conditions based on the local climate and to assess the need for regional heat-safety guidelines.   Cross-sectional study.   Data from incidents of fatal exertional heat stroke (EHS) in American football players were obtained from the National Center for Catastrophic Sport Injury Research and the Korey Stringer Institute.   Sixty-one American football players at all levels of competition with fatal EHSs from 1980 to 2014.   We used the wet bulb globe temperature (WBGT) and a z-score WBGT standardized to local climate conditions from 1991 to 2010 to assess the absolute and relative magnitudes of heat stress, respectively.   We observed a poleward decrease in exposure WBGTs during fatal EHSs. In milder climates, 80% of cases occurred at above-average WBGTs, and 50% occurred at WBGTs greater than 1 standard deviation from the long-term mean; however, in hotter climates, half of the cases occurred at near average or below average WBGTs.   The combination of lower exposure WBGTs and frequent extreme climatic values in milder climates during fatal EHSs indicates the need for regional activity-modification guidelines with lower, climatically appropriate weather-based thresholds. Established activity-modification guidelines, such as those from the American College of Sports Medicine, work well in the hotter climates, such as the southern United States, where hot and humid weather conditions are common.

Fabrication, modification, and application of poly(methyl methacrylate) microfluidic chips.

PubMed

Chen, Yun; Zhang, Luyan; Chen, Gang

2008-05-01

Poly(methyl methacrylate) (PMMA) is particularly useful for microfluidic chips with the features of low price, excellent optic transparency, attractive mechanical and chemical properties, ease of fabrication and modification, biocompatibility, etc. During the past decade, significant progress in the PMMA microfluidic chips has occurred. This review, which contains 120 references, summarizes the recent advances and the key strategies in the fabrication, modification, and application of PMMA microfluidic chips. It is expected that PMMA microchips should find a wide range of applications and will lead to the creation of truly disposable microfluidic devices.

TiO2 induced structural modifications in Cs containing borosilicate glasses: Raman and infrared studies

NASA Astrophysics Data System (ADS)

Pandey, M.; Banerjee, D.; Sudarsan, V.; Kshirsagar, R. J.

2018-04-01

Effect of TiO2 addition in Cs containing Sodium-borosilicate glasses is studied using Raman and infrared spectroscopic techniques. As revealed from infrared and Raman studies, TiO2 does not form segregated phase, but instead enters into the borosilicate network. It is further observed that TiO2 addition results in modifications of the borate and silicate structural units by transforming into tetraborates and metasilicate structural units. These structural modifications are responsible for Cs immobilization, leach rate and chemical durability of these glasses.

Update: Mechanisms underlying N6-methyladenosine modification of eukaryotic mRNA

PubMed Central

Wang, Yang; Zhao, Jing Crystal

2016-01-01

Summary Eukaryotic messenger RNA (mRNA) undergoes chemical modification both at the 5′cap [1, 2] and internally [3–14]. Among internal modifications, m6A, by far the most abundant, is present in all eukaryotes examined, including mammals [3–6], flies [15], plants [16, 17] and yeast [18, 19]. m6A modification plays an essential role in diverse biological processes. Over the past few years, our knowledge relevant to establishment and function of this modification has grown rapidly. This review focuses on technologies that have facilitated m6A detection in mRNAs, identification of m6A methylation enzymes and binding proteins, and potential functions of the modification at the molecular level. Regarding m6A function at cellular or organismal levels or in disease, please refer to other recent reviews [20–23]. PMID:27793360

Protein mass analysis of histones.

PubMed

Galasinski, Scott C; Resing, Katheryn A; Ahn, Natalie G

2003-09-01

Posttranslational modification of chromatin-associated proteins, including histones and high-mobility-group (HMG) proteins, provides an important mechanism to control gene expression, genome integrity, and epigenetic inheritance. Protein mass analysis provides a rapid and unbiased approach to monitor multiple chemical modifications on individual molecules. This review describes methods for acid extraction of histones and HMG proteins, followed by separation by reverse-phase chromatography coupled to electrospray ionization mass spectrometry (LC/ESI-MS). Posttranslational modifications are detected by analysis of full-length protein masses. Confirmation of protein identity and modification state is obtained through enzymatic digestion and peptide sequencing by MS/MS. For differentially modified forms of each protein, the measured intensities are semiquantitative and allow determination of relative abundance and stoichiometry. The method simultaneously detects covalent modifications on multiple proteins and provides a facile assay for comparing chromatin modification states between different cell types and/or cellular responses.

The Expanding Landscape of the Thiol Redox Proteome*

PubMed Central

Yang, Jing; Carroll, Kate S.; Liebler, Daniel C.

2016-01-01

Cysteine occupies a unique place in protein chemistry. The nucleophilic thiol group allows cysteine to undergo a broad range of redox modifications beyond classical thiol-disulfide redox equilibria, including S-sulfenylation (-SOH), S-sulfinylation (-SO2H), S-sulfonylation (-SO3H), S-nitrosylation (-SNO), S-sulfhydration (-SSH), S-glutathionylation (-SSG), and others. Emerging evidence suggests that these post-translational modifications (PTM) are important in cellular redox regulation and protection against oxidative damage. Identification of protein targets of thiol redox modifications is crucial to understanding their roles in biology and disease. However, analysis of these highly labile and dynamic modifications poses challenges. Recent advances in the design of probes for thiol redox forms, together with innovative mass spectrometry based chemoproteomics methods make it possible to perform global, site-specific, and quantitative analyses of thiol redox modifications in complex proteomes. Here, we review chemical proteomic strategies used to expand the landscape of thiol redox modifications. PMID:26518762

Quantitative PCR measurement of tRNA 2-methylthio modification for assessing type 2 diabetes risk.

PubMed

Xie, Peiyu; Wei, Fan-Yan; Hirata, Shoji; Kaitsuka, Taku; Suzuki, Tsutomu; Suzuki, Takeo; Tomizawa, Kazuhito

2013-11-01

Genetic variants in the human CDKAL1 (CDK5 regulatory subunit associated protein 1-like 1) gene have been associated with reduced insulin secretion and type 2 diabetes (T2D). CDKAL1 is a methylthiotransferase that catalyzes 2-methylthio (ms(2)) modification of the adenine at position 37 (A37) of cytoplasmic tRNA(Lys)(UUU). We investigated the ms(2)-modification level of tRNA(Lys)(UUU) as a direct readout of CDKAL1 enzyme activity in human samples. We developed a quantitative PCR (qPCR)-based method to measure ms(2) modification. tRNA(Lys)(UUU) was reverse-transcribed with 2 unique primers: Reverse primer r1 was designed to anneal to the middle of this tRNA, including the nucleotide at A37, and reverse primer r2 was designed to anneal to the region downstream (3') of A37. Subsequent qPCR was performed to detect the corresponding transcribed cDNAs. The efficiency of reverse transcription of tRNA(Lys)(UUU) was ms(2)-modification dependent. The relative difference in threshold cycle number obtained with the r1 or r2 primer yielded the ms(2)-modification level in tRNA(Lys)(UUU) precisely as predicted by an original mathematical model. The method was capable of measuring ms(2)-modification levels in tRNA(Lys)(UUU) in total RNA isolated from human peripheral blood samples, revealing that the ms(2)-modification rate in tRNA(Lys)(UUU) was decreased in individuals carrying the CDKAL1 genotype associated with T2D. In addition, the ms(2)-modification level was correlated with insulin secretion. The results point to the critical role of ms(2) modification in T2D and to a potential clinical use of a simple and high-throughput method for assessing T2D risk.

Posttranslational Modifications Regulate the Postsynaptic Localization of PSD-95.

PubMed

Vallejo, Daniela; Codocedo, Juan F; Inestrosa, Nibaldo C

2017-04-01

The postsynaptic density (PSD) consists of a lattice-like array of interacting proteins that organizes and stabilizes synaptic receptors, ion channels, structural proteins, and signaling molecules required for normal synaptic transmission and synaptic function. The scaffolding and hub protein postsynaptic density protein-95 (PSD-95) is a major element of central chemical synapses and interacts with glutamate receptors, cell adhesion molecules, and cytoskeletal elements. In fact, PSD-95 can regulate basal synaptic stability as well as the activity-dependent structural plasticity of the PSD and, therefore, of the excitatory chemical synapse. Several studies have shown that PSD-95 is highly enriched at excitatory synapses and have identified multiple protein structural domains and protein-protein interactions that mediate PSD-95 function and trafficking to the postsynaptic region. PSD-95 is also a target of several signaling pathways that induce posttranslational modifications, including palmitoylation, phosphorylation, ubiquitination, nitrosylation, and neddylation; these modifications determine the synaptic stability and function of PSD-95 and thus regulate the fates of individual dendritic spines in the nervous system. In the present work, we review the posttranslational modifications that regulate the synaptic localization of PSD-95 and describe their functional consequences. We also explore the signaling pathways that induce such changes.

Mechanistic understanding of the cysteine capping modifications of antibodies enables selective chemical engineering in live mammalian cells.

PubMed

Zhong, Xiaotian; He, Tao; Prashad, Amar S; Wang, Wenge; Cohen, Justin; Ferguson, Darren; Tam, Amy S; Sousa, Eric; Lin, Laura; Tchistiakova, Lioudmila; Gatto, Scott; D'Antona, Aaron; Luan, Yen-Tung; Ma, Weijun; Zollner, Richard; Zhou, Jing; Arve, Bo; Somers, Will; Kriz, Ronald

2017-04-20

Protein modifications by intricate cellular machineries often redesign the structure and function of existing proteins to impact biological networks. Disulfide bond formation between cysteine (Cys) pairs is one of the most common modifications found in extracellularly-destined proteins, key to maintaining protein structure. Unpaired surface cysteines on secreted mammalian proteins are also frequently found disulfide-bonded with free Cys or glutathione (GSH) in circulation or culture, the mechanism for which remains unknown. Here we report that these so-called Cys-capping modifications take place outside mammalian cells, not in the endoplasmic reticulum (ER) where oxidoreductase-mediated protein disulfide formation occurs. Unpaired surface cysteines of extracellularly-arrived proteins such as antibodies are uncapped upon secretion before undergoing disulfide exchange with cystine or oxidized GSH in culture medium. This observation has led to a feasible way to selectively modify the nucleophilic thiol side-chain of cell-surface or extracellular proteins in live mammalian cells, by applying electrophiles with a chemical handle directly into culture medium. These findings provide potentially an effective approach for improving therapeutic conjugates and probing biological systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Genetic modification of plant cell walls to enhance biomass yield and biofuel production in bioenergy crops.

PubMed

Wang, Yanting; Fan, Chunfen; Hu, Huizhen; Li, Ying; Sun, Dan; Wang, Youmei; Peng, Liangcai

2016-01-01

Plant cell walls represent an enormous biomass resource for the generation of biofuels and chemicals. As lignocellulose property principally determines biomass recalcitrance, the genetic modification of plant cell walls has been posed as a powerful solution. Here, we review recent progress in understanding the effects of distinct cell wall polymers (cellulose, hemicelluloses, lignin, pectin, wall proteins) on the enzymatic digestibility of biomass under various physical and chemical pretreatments in herbaceous grasses, major agronomic crops and fast-growing trees. We also compare the main factors of wall polymer features, including cellulose crystallinity (CrI), hemicellulosic Xyl/Ara ratio, monolignol proportion and uronic acid level. Furthermore, the review presents the main gene candidates, such as CesA, GH9, GH10, GT61, GT43 etc., for potential genetic cell wall modification towards enhancing both biomass yield and enzymatic saccharification in genetic mutants and transgenic plants. Regarding cell wall modification, it proposes a novel groove-like cell wall model that highlights to increase amorphous regions (density and depth) of the native cellulose microfibrils, providing a general strategy for bioenergy crop breeding and biofuel processing technology. Copyright © 2016 Elsevier Inc. All rights reserved.

Biocatalysts with enhanced inhibitor tolerance

DOEpatents

Yang, Shihui; Linger, Jeffrey; Franden, Mary Ann; Pienkos, Philip T.; Zhang, Min

2015-12-08

Disclosed herein are biocatalysts for the production of biofuels, including microorganisms that contain genetic modifications conferring tolerance to growth and fermentation inhibitors found in many cellulosic feedstocks. Methods of converting cellulose-containing materials to fuels and chemicals, as well as methods of fermenting sugars to fuels and chemicals, using these biocatalysts are also disclosed.

Chemical Modification of Kraft Lignin: Effect on Chemical and Thermal Properties

Treesearch

Yao Chen; Nicole M. Stark; Zhiyong Cai; Charles R. Frihart; Linda F. Lorenz; Rebecca E. Ibach

2014-01-01

Esterified kraft lignins (KL) were prepared by reaction with maleic anhydride (MA), succinic anhydride (SA), and phthalic anhydride (PA) in acetone solutions. The esterified lignins were characterized using ATR-FTIR, solid state CP-MAS 13C NMR spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). PA...

The evolution of adenoviral vectors through genetic and chemical surface modifications.

PubMed

Capasso, Cristian; Garofalo, Mariangela; Hirvinen, Mari; Cerullo, Vincenzo

2014-02-17

A long time has passed since the first clinical trial with adenoviral (Ad) vectors. Despite being very promising, Ad vectors soon revealed their limitations in human clinical trials. The pre-existing immunity, the marked liver tropism and the high toxicity of first generation Ad (FG-Ad) vectors have been the main challenges for the development of new approaches. Significant effort toward the development of genetically and chemically modified adenoviral vectors has enabled researchers to create more sophisticated vectors for gene therapy, with an improved safety profile and a higher transduction ability of different tissues. In this review, we will describe the latest findings in the high-speed, evolving field of genetic and chemical modifications of adenoviral vectors, a field in which different disciplines, such as biomaterial research, virology and immunology, co-operate synergistically to create better gene therapy tools for modern challenges.

Improving lead adsorption through chemical modification of wheat straw by lactic acid

NASA Astrophysics Data System (ADS)

Mu, Ruimin; Wang, Minxiang; Bu, Qingwei; Liu, Dong; Zhao, Yanli

2018-01-01

This work describes the creation of a new cellulosic material derived from wheat straw modified by lactic acid for adsorption of lead in aqueous solution, called 0.3LANS (the concentration of the lactic acid were 0.3mol/L). Batch experiments were conducted to study the effects of initial pH value, contact time, adsorbent dose, initial concentration and temperature. Fourier transform infrared (FTIR), Elemental analysis, BET surface area and Scanning electron micrographs (SEM) analysis were used to investigate the chemical modification. Adsorption isotherm models namely, Langmuir, Freundlich were used to analyse the equilibrium data, and the Langmuir isotherm model provided the best correlation, means that the adsorption was chemical monolayer adsorption and the adsorption capacity qm was increased with increasing temperature, and reached 51.49mg/g for 0.3LANS at 35°C, showing adsorption was exothermic.

Worldwide occurrence of silica-rich melts in sub-continental and sub-oceanic mantle minerals

NASA Astrophysics Data System (ADS)

Schiano, P.; Clocchiatti, R.

1994-04-01

ROCK samples derived from the Earth's upper mantle commonly show indirect evidence for chemical modification. Such modification, or 'metasomatism', can be recognized by the precipitation of exotic minerals such as phlogopite, amphibole or apatite1, and by the overprinting of the bulk compositions of the mantle rocks by a chemical signature involving the enrichment of potassium and other 'incompatible' elements2. Here we study the composition of the metasomatic agents more directly by examining melt and fluid inclusions trapped in mantle minerals. These inclusions are secondary, forming trails along healed fracture planes. A systematic study of the chemical compositions and entrapment temperatures and pressures of inclusions from 14 ultramaflc peridotites from both continental and oceanic intraplate regions shows that volatile- and silica-rich metasomatic melts are present throughout the litho-sphere. Their compositions, which differ dramatically from those of erupted, mantle-derived magmas, are more akin to continental than to oceanic crust.

Investigation of Sterilization Mechanism for Geobacillus stearothermophilus Spores with Plasma-Excited Neutral Gas

NASA Astrophysics Data System (ADS)

Matsui, Kei; Ikenaga, Noriaki; Sakudo, Noriyuki

2015-09-01

We investigate the mechanism of the sterilization with plasma-excited neutral gas that uniformly sterilizes both the space and inner wall of the reactor chamber at atmospheric pressure. Only reactive neutral species such as plasma-excited gas molecules and radicals are separated from the plasma and sent to the reactor chamber for chemical sterilization. The plasma source gas uses humidified mixture of nitrogen and oxygen. Geobacillus stearothermophilus spores and tyrosine which is amino acid are treated by the plasma-excited neutral gas. Shape change of the treated spore is observed by SEM, and chemical modification of the treated tyrosine is analyzed by HPLC. As a result, the surface of the treated spore shows depression. Hydroxylation and nitration of tyrosine are shown after the treatment. For these reasons, we believe that the sterilization with plasma-excited neutral gas results from the deformation of spore structure due to the chemical modification of amino acid.

Total chemical synthesis of modified histones

NASA Astrophysics Data System (ADS)

Qi, Yun-Kun; Ai, Hua-Song; Li, Yi-Ming; Yan, Baihui

2018-02-01

In the post-genome era, epigenetics has received increasing attentions in recent years. The post-translational modifications (PTMs) of four core histones play central roles in epigenetic regulation of eukaryotic genome by either directly altering the biophysical properties of nucleosomes or by recruiting other effector proteins. In order to study the biological functions and structural mechanisms of these histone PTMs, an obligatory step is to prepare a sufficient amount of homogeneously modified histones. This task cannot be fully accomplished either by recombinant technology or enzymatic modification. In this context, synthetic chemists have developed novel protein synthetic tools and state-of-the-art chemical ligation strategies for the preparation of homologous modified histones. In this review, we summarize the recent advances in the preparation of modified histones, focusing on the total chemical synthesis strategies. The importance and potential of synthetic chemistry for the study of histone code will be also discussed.

Future Needs and Recommendations in the Development of Species Sensitivity Distributions: Estimating Toxicity Thresholds for Aquatic Ecological Communities and Assessing Impacts of Chemical Exposures

EPA Science Inventory

A species sensitivity distribution (SSD) is a probability model of the variation of species sensitivities to a stressor, in particular chemical exposure. The SSD approach has been used as a decision support tool in environmental protection and management since the 1980s, and the ...

Plasma assisted surface coating/modification processes - An emerging technology

NASA Technical Reports Server (NTRS)

Spalvins, T.

1987-01-01

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation. These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Plasma assisted surface coating/modification processes: An emerging technology

NASA Technical Reports Server (NTRS)

Spalvins, T.

1986-01-01

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation). These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Influence of the chemical structure on odor qualities and odor thresholds of halogenated guaiacol-derived odorants

NASA Astrophysics Data System (ADS)

Juhlke, Florian; Lorber, Katja; Wagenstaller, Maria; Buettner, Andrea

2017-12-01

Chlorinated guaiacol derivatives are found in waste water of pulp mills using chlorine in the bleaching process of wood pulp. They can also be detected in fish tissue, possibly causing off-odors. To date, there is no systematic investigation on the odor properties of halogenated guaiacol derivatives. To close this gap, odor thresholds in air and odor qualities of 14 compounds were determined by gas chromatography-olfactometry. Overall, the investigated compounds elicited smells that are characteristic for guaiacol, namely smoky, sweet, vanilla-like, but also medicinal and plaster-like. Their odor thresholds in air were, however, very low, ranging from 0.00072 to 23 ng/Lair. The lowest thresholds were found for 5-chloro- and 5-bromoguaiacol, followed by 4,5-dichloro- and 6-chloroguaiacol. Moreover, some inter-individual differences in odor threshold values could be observed, with the highest variations having been recorded for the individual values of 5-iodo- and 4-bromoguaiacol.

Effect of Carboxymethylation on the Rheological Properties of Hyaluronan

PubMed Central

Wendling, Rian J.; Christensen, Amanda M.; Quast, Arthur D.; Atzet, Sarah K.; Mann, Brenda K.

2016-01-01

Chemical modifications made to hyaluronan to enable covalent crosslinking to form a hydrogel or to attach other molecules may alter the physical properties as well, which have physiological importance. Here we created carboxymethyl hyaluronan (CMHA) with varied degree of modification and investigated the effect on the viscosity of CMHA solutions. Viscosity decreased initially as modification increased, with a minimum viscosity for about 30–40% modification. This was followed by an increase in viscosity around 45–50% modification. The pH of the solution had a variable effect on viscosity, depending on the degree of carboxymethyl modification and buffer. The presence of phosphates in the buffer led to decreased viscosity. We also compared large-scale production lots of CMHA to lab-scale and found that large-scale required extended reaction times to achieve the same degree of modification. Finally, thiolated CMHA was disulfide crosslinked to create hydrogels with increased viscosity and shear-thinning aspects compared to CMHA solutions. PMID:27611817

Celebrating wobble decoding: Half a century and still much is new.

PubMed

Agris, Paul F; Eruysal, Emily R; Narendran, Amithi; Väre, Ville Y P; Vangaveti, Sweta; Ranganathan, Srivathsan V

2017-08-16

A simple post-transcriptional modification of tRNA, deamination of adenosine to inosine at the first, or wobble, position of the anticodon, inspired Francis Crick's Wobble Hypothesis 50 years ago. Many more naturally-occurring modifications have been elucidated and continue to be discovered. The post-transcriptional modifications of tRNA's anticodon domain are the most diverse and chemically complex of any RNA modifications. Their contribution with regards to chemistry, structure and dynamics reveal individual and combined effects on tRNA function in recognition of cognate and wobble codons. As forecast by the Modified Wobble Hypothesis 25 years ago, some individual modifications at tRNA's wobble position have evolved to restrict codon recognition whereas others expand the tRNA's ability to read as many as four synonymous codons. Here, we review tRNA wobble codon recognition using specific examples of simple and complex modification chemistries that alter tRNA function. Understanding natural modifications has inspired evolutionary insights and possible innovation in protein synthesis.

Simple Fabrication of Gd(III)-DTPA-Nanodiamond Particles by Chemical Modification for Use as Magnetic Resonance Imaging (MRI) Contrast Agent

NASA Astrophysics Data System (ADS)

Nakamura, Takako; Ohana, Tsuguyori; Yabuno, Hajime; Kasai, Rumiko; Suzuki, Tetsuya; Hasebe, Terumitsu

2013-01-01

We have developed a simple and useful process for fabricating nanodiamond (ND) particles modified with an organogadolinium moiety by chemical modification for their use as a magnetic resonance imaging (MRI) contrast agent. The introduction of the organogadolinium moiety on the surface of the ND particles was performed by the condensation of ND and diethylenetriaminepentaacetic acid (DTPA) followed by treatment with GdCl3. The modified surfaces were evaluated by X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, mass spectroscopy, and inductively coupled plasma atomic emission spectroscopy analyses. MRI experiments on the Gd-DTPA-ND particles indicated their high signal intensity on T1-weighted images.

Functional Assessment of Laser Irradiation.

DTIC Science & Technology

1988-03-01

shock altogether. Following shaping, threshold acuity testing was derived using a modification of the von Bekesy tracking technique (14). In this...burns produced by atomic flash. AMA Arch. Ophthal 53: 351-364 (1955) 2. Hawerth, R.S. and Sperling , H.G. Prolonged color blindness induced by intense...Swinnen, M.E.T., Brady, J.V. & Powell, M.G. A new device for the application of shock. Behav. Meth. & Instrum 1: 184 (1969) 14. Bekesy, G. von . A new

The Actions of Lyophilized Apple Peel on the Electrical Activity and Organization of the Ventricular Syncytium of the Hearts of Diabetic Rats

PubMed Central

Martínez-Ladrón de Guevara, Elideth; Pérez-Hernández, Nury; Villalobos-López, Miguel Ángel; Pérez-Ishiwara, David Guillermo; Salas-Benito, Juan Santiago; Martínez Martínez, Alejandro; Hernández-García, Vicente

2016-01-01

This study was designed to examine the effects of lyophilized red delicious apple peel (RDP) on the action potentials (APs) and the input resistance-threshold current relationship. The experiments were performed on isolated papillary heart muscles from healthy male rats, healthy male rats treated with RDP, diabetic male rats, and diabetic male rats treated with RDP. The preparation was superfused with oxygenated Tyrode's solution at 37°C. The stimulation and the recording of the APs, the input resistance, and the threshold current were made using conventional electrophysiological methods. The RDP presented no significant effect in normal rats. Equivalent doses in diabetic rats reduced the APD and ARP. The relationship between input resistance and threshold current established an inverse correlation. The results indicate the following: (1) The functional structure of the cardiac ventricular syncytium in healthy rats is heterogeneous, in terms of input resistance and threshold current. Diabetes further accentuates the heterogeneity. (2) As a consequence, conduction block occurs and increases the possibility of reentrant arrhythmias. (3) These modifications in the ventricular syncytium, coupled with the increase in the ARP, are the adequate substrate so that, with diabetes, the heart becomes more arrhythmogenic. (4) RDP decreases the APD, the ARP, and most syncytium irregularity caused by diabetes. PMID:26839897

Development and application of an innovative expert decision support system to manage sediments and to assess environmental risk in freshwater ecosystems.

PubMed

Dagnino, Alessandro; Bo, Tiziano; Copetta, Andrea; Fenoglio, Stefano; Oliveri, Caterina; Bencivenga, Mauro; Felli, Angelo; Viarengo, Aldo

2013-10-01

With the aim of supporting decision makers to manage contamination in freshwater environments, an innovative expert decision support system (EDSS) was developed. The EDSS was applied in a sediment quality assessment along the Bormida river (NW, Italy) which has been heavily contaminated by an upstream industrial site for more than a century. Sampling sites were classified by means of comparing chemical concentrations with effect-based target values (threshold and probable effect concentrations). The level of each contaminant and the combined toxic pressure were used to rank sites into three categories: (i) uncontaminated (8 sites), (ii) mildly contaminated (4) and (iii) heavily contaminated (19). In heavily contaminated sediments, an environmental risk index (EnvRI) was determined by means of integrating chemical data with ecotoxicological and ecological parameters (triad approach). In addition a sediment risk index (SedRI) was computed from combining chemical and ecotoxicological data. Eight sites exhibited EnvRI values ≥0.25, the safety threshold level (range of EnvRI values: 0.14-0.31) whereas SedRI exceeded the safety threshold level at 6 sites (range of SedRI values: 0.16-0.36). At sites classified as mildly contaminated, sublethal biomarkers were integrated with chemical data into a biological vulnerability index (BVI), which exceeded the safety threshold level at one site (BVI value: 0.28). Finally, potential human risk was assessed in selected stations (11 sites) by integrating genotoxicity biomarkers (GTI index falling in the range 0.00-0.53). General conclusions drawn from the EDSS data include: (i) in sites classified as heavily contaminated, only a few exhibited some significant, yet limited, effects on biodiversity; (ii) restrictions in re-using sediments from heavily contaminated sites found little support in ecotoxicological data; (iii) in the majority of the sites classified as mildly contaminated, tested organisms exhibited low response levels; (iv) preliminary results on genotoxicity biomarkers indicate possible negative consequences for humans if exposed to river sediments from target areas. © 2013.

Differential reconstructed gene interaction networks for deriving toxicity threshold in chemical risk assessment.

PubMed

Yang, Yi; Maxwell, Andrew; Zhang, Xiaowei; Wang, Nan; Perkins, Edward J; Zhang, Chaoyang; Gong, Ping

2013-01-01

Pathway alterations reflected as changes in gene expression regulation and gene interaction can result from cellular exposure to toxicants. Such information is often used to elucidate toxicological modes of action. From a risk assessment perspective, alterations in biological pathways are a rich resource for setting toxicant thresholds, which may be more sensitive and mechanism-informed than traditional toxicity endpoints. Here we developed a novel differential networks (DNs) approach to connect pathway perturbation with toxicity threshold setting. Our DNs approach consists of 6 steps: time-series gene expression data collection, identification of altered genes, gene interaction network reconstruction, differential edge inference, mapping of genes with differential edges to pathways, and establishment of causal relationships between chemical concentration and perturbed pathways. A one-sample Gaussian process model and a linear regression model were used to identify genes that exhibited significant profile changes across an entire time course and between treatments, respectively. Interaction networks of differentially expressed (DE) genes were reconstructed for different treatments using a state space model and then compared to infer differential edges/interactions. DE genes possessing differential edges were mapped to biological pathways in databases such as KEGG pathways. Using the DNs approach, we analyzed a time-series Escherichia coli live cell gene expression dataset consisting of 4 treatments (control, 10, 100, 1000 mg/L naphthenic acids, NAs) and 18 time points. Through comparison of reconstructed networks and construction of differential networks, 80 genes were identified as DE genes with a significant number of differential edges, and 22 KEGG pathways were altered in a concentration-dependent manner. Some of these pathways were perturbed to a degree as high as 70% even at the lowest exposure concentration, implying a high sensitivity of our DNs approach. Findings from this proof-of-concept study suggest that our approach has a great potential in providing a novel and sensitive tool for threshold setting in chemical risk assessment. In future work, we plan to analyze more time-series datasets with a full spectrum of concentrations and sufficient replications per treatment. The pathway alteration-derived thresholds will also be compared with those derived from apical endpoints such as cell growth rate.

DMS-MaPseq for genome-wide or targeted RNA structure probing in vivo.

PubMed

Zubradt, Meghan; Gupta, Paromita; Persad, Sitara; Lambowitz, Alan M; Weissman, Jonathan S; Rouskin, Silvi

2017-01-01

Coupling of structure-specific in vivo chemical modification to next-generation sequencing is transforming RNA secondary structure studies in living cells. The dominant strategy for detecting in vivo chemical modifications uses reverse transcriptase truncation products, which introduce biases and necessitate population-average assessments of RNA structure. Here we present dimethyl sulfate (DMS) mutational profiling with sequencing (DMS-MaPseq), which encodes DMS modifications as mismatches using a thermostable group II intron reverse transcriptase. DMS-MaPseq yields a high signal-to-noise ratio, can report multiple structural features per molecule, and allows both genome-wide studies and focused in vivo investigations of even low-abundance RNAs. We apply DMS-MaPseq for the first analysis of RNA structure within an animal tissue and to identify a functional structure involved in noncanonical translation initiation. Additionally, we use DMS-MaPseq to compare the in vivo structure of pre-mRNAs with their mature isoforms. These applications illustrate DMS-MaPseq's capacity to dramatically expand in vivo analysis of RNA structure.

Chemical Approaches for Structure and Function of RNA in Postgenomic Era

PubMed Central

Ro-Choi, Tae Suk; Choi, Yong Chun

2012-01-01

In the study of cellular RNA chemistry, a major thrust of research focused upon sequence determinations for decades. Structures of snRNAs (4.5S RNA I (Alu), U1, U2, U3, U4, U5, and U6) were determined at Baylor College of Medicine, Houston, Tex, in an earlier time of pregenomic era. They show novel modifications including base methylation, sugar methylation, 5′-cap structures (types 0–III) and sequence heterogeneity. This work offered an exciting problem of posttranscriptional modification and underwent numerous significant advances through technological revolutions during pregenomic, genomic, and postgenomic eras. Presently, snRNA research is making progresses involved in enzymology of snRNA modifications, molecular evolution, mechanism of spliceosome assembly, chemical mechanism of intron removal, high-order structure of snRNA in spliceosome, and pathology of splicing. These works are destined to reach final pathway of work “Function and Structure of Spliceosome” in addition to exciting new exploitation of other noncoding RNAs in all aspects of regulatory functions. PMID:22347623

Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction.

PubMed

Tajima, Kenji; Iwamoto, Kosuke; Satoh, Yasuharu; Sakai, Ryosuke; Satoh, Toshifumi; Dairi, Tohru

2016-05-01

Polyhydroxyalkanoates (PHAs) incorporating vinyl-bearing 3-hydroxyalkanoates were prepared in 8.5-12.9 g L(-1) yield. The molar ratios (0-16 mol%) of the vinyl-bearing 3-hydroxyalkanoate derivatives were controlled by the continuous feeding of undecylenate at various concentrations. Subsequently, the PHAs were functionalized by UV-initiated thiol-ene click reaction and chemical modification. (1)H NMR spectra suggested that 3-mercaptopropionic acid and 2-aminoethanethiol were successfully introduced into the vinyl-bearing PHA. Subsequently, chemical modification using fluorescein or a fibronectin active fragment (GRGDS) was attempted. The former yielded a PHA derivative capable of emitting fluorescence under UV irradiation, which was useful for determining the miscibility of PHA in a composite film comprising poly-ʟ-lactic acid (PLLA) and PHA. In the latter case, PHA bearing GRGDS peptides exhibited cell adhesiveness, suggesting that its biocompatibility was improved upon peptide introduction. Taken together, the UV-initiated thiol-ene click reaction was demonstrated to be useful in PHA modification.

Mixed mechanisms of multi-site phosphorylation

PubMed Central

Suwanmajo, Thapanar; Krishnan, J.

2015-01-01

Multi-site phosphorylation is ubiquitous in cell biology and has been widely studied experimentally and theoretically. The underlying chemical modification mechanisms are typically assumed to be distributive or processive. In this paper, we study the behaviour of mixed mechanisms that can arise either because phosphorylation and dephosphorylation involve different mechanisms or because phosphorylation and/or dephosphorylation can occur through a combination of mechanisms. We examine a hierarchy of models to assess chemical information processing through different mixed mechanisms, using simulations, bifurcation analysis and analytical work. We demonstrate how mixed mechanisms can show important and unintuitive differences from pure distributive and processive mechanisms, in some cases resulting in monostable behaviour with simple dose–response behaviour, while in other cases generating new behaviour-like oscillations. Our results also suggest patterns of information processing that are relevant as the number of modification sites increases. Overall, our work creates a framework to examine information processing arising from complexities of multi-site modification mechanisms and their impact on signal transduction. PMID:25972433

Molecular modification of highly degenerate semiconductor as an active electrode to enhance the performance of supercapacitors

NASA Astrophysics Data System (ADS)

Mundinamani, S. P.; Rabinal, M. K.

2014-12-01

Highly conducting antimony doped tin oxide (SnO2:Sb) films are electrografted with suitable organic molecules to study their electrolytic behavior. A series of organic molecules, such as heptanethiol, dodecanethiol and octadecanethiol are bonded to electrode surfaces. Electrolytic capacitors were formed on both unmodified and chemically modified electrodes using KCl and H2SO4 as electrolytes. This molecular modification significantly enhances the current levels in cyclic voltammograms, and there is a clear shift in oxidation/reduction peaks of these capacitors with scan rate. The results obey Randles-Sevcik relation, which indicates that there is enhancement of ionic diffusion at the electrode-electrolyte interface. There is a large enhancement in the values of specific capacitance (almost by 104 times) after the chemical modification. These measurements show that Faradaic reactions are responsible for charge storage/discharge process in these capacitors. Hence, the molecularly modified electrodes can be a good choice to increase the specific capacitance.

Modified polyether-sulfone membrane: a mini review

PubMed Central

Alenazi, Noof A.; Hussein, Mahmoud A.; Alamry, Khalid A.; Asiri, Abdullah M.

2017-01-01

Abstract Polyethersulfone has been widely used as a promising material in medical applications and waste-treatment membranes since it provides excellent mechanical and thermal properties. Hydrophobicity of polyethersulfone is considered one main disadvantage of using this material because hydrophobic surface causes biofouling effects to the membrane which is always thought to be a serious limitation to the use of polyethersulfone in membrane technology. Chemical modification to the material is a promising solution to this problem. More specifically surface modification is an excellent technique to introduce hydrophilic properties and functional groups to the polyethersulfone membrane surface. This review covers chemical modifications of the polyethersulfone and covers different methods used to enhance the hydrophilicity of polyethersulfone membrane. In particular, the addition of amino functional groups to polyethersulfone is used as a fundamental method either to introduce hydrophilic properties or introduce nanomaterials to the surface of polyethersulfone membrane. This work reviews also previous research reports explored the use of amino functionalized polyethersulfone with different nanomaterials to induce biological activity and reduce fouling effects of the fabricated membrane. PMID:29491825

Surface modification of biomaterials using plasma immersion ion implantation and deposition

PubMed Central

Lu, Tao; Qiao, Yuqin; Liu, Xuanyong

2012-01-01

Although remarkable progress has been made on biomaterial research, the ideal biomaterial that satisfies all the technical requirements and biological functions is not available up to now. Surface modification seems to be a more economic and efficient way to adjust existing conventional biomaterials to meet the current and ever-evolving clinical needs. From an industrial perspective, plasma immersion ion implantation and deposition (PIII&D) is an attractive method for biomaterials owing to its capability of treating objects with irregular shapes, as well as the control of coating composition. It is well acknowledged that the physico-chemical characteristics of biomaterials are the decisive factors greatly affecting the biological responses of biomaterials including bioactivity, haemocompatibility and antibacterial activity. Here, we mainly review the recent advances in surface modification of biomaterials via PIII&D technology, especially titanium alloys and polymers used for orthopaedic, dental and cardiovascular implants. Moreover, the variations of biological performances depending on the physico-chemical properties of modified biomaterials will be discussed. PMID:23741609

Effects of Site-Specific Guanine C8-Modifications on an Intramolecular DNA G-Quadruplex

PubMed Central

Lech, Christopher Jacques; Cheow Lim, Joefina Kim; Wen Lim, Jocelyn Mei; Amrane, Samir; Heddi, Brahim; Phan, Anh Tuân

2011-01-01

Understanding the fundamentals of G-quadruplex formation is important both for targeting G-quadruplexes formed by natural sequences and for engineering new G-quadruplexes with desired properties. Using a combination of experimental and computational techniques, we have investigated the effects of site-specific substitution of a guanine with C8-modified guanine derivatives, including 8-bromo-guanine, 8-O-methyl-guanine, 8-amino-guanine, and 8-oxo-guanine, within a well-defined (3 + 1) human telomeric G-quadruplex platform. The effects of substitutions on the stability of the G-quadruplex were found to depend on the type and position of the modification among different guanines in the structure. An interesting modification-dependent NMR chemical-shift effect was observed across basepairing within a guanine tetrad. This effect was reproduced by ab initio quantum mechanical computations, which showed that the observed variation in imino proton chemical shift is largely influenced by changes in hydrogen-bond geometry within the guanine tetrad. PMID:22004753

[Effect of acetylation and oxidation on some properties of breadfruit (Artocarpus altilis) seed starch].

PubMed

Rincón, Alicia Mariela; Bou Rached, Lizet; Aragoza, Luis E; Padilla, Fanny

2007-09-01

Starch extracted from seeds of Artocarpus altilis (Breadfruit) was chemically modified by acetylation and oxidation, and its functional properties were evaluated and compared with these of native starch. Analysis of the chemical composition showed that moisture content was higher for modified starches. Ash, protein, crude fiber and amylose contents were reduced by the modifications, but did not alter the native starch granules' irregularity, oval shape and smooth surface. Acetylation produced changes in water absorption, swelling power and soluble solids, these values were higher for acetylated starch, while values for native and oxidized starches were similar. Both modifications reduced pasting temperature; oxidation reduced maximum peak viscosity but it was increased by acetylation. Hot paste viscosity was reduced by both modifications, whereas cold paste viscosity was lower in the oxidized starch and higher in the acetylated starch. Breakdown was increased by acetylation and reduced with oxidation. Setback value was reduced after acetylation, indicating it could minimize retrogradation of the starch.

Modified polyether-sulfone membrane: a mini review.

PubMed

Alenazi, Noof A; Hussein, Mahmoud A; Alamry, Khalid A; Asiri, Abdullah M

2017-01-01

Polyethersulfone has been widely used as a promising material in medical applications and waste-treatment membranes since it provides excellent mechanical and thermal properties. Hydrophobicity of polyethersulfone is considered one main disadvantage of using this material because hydrophobic surface causes biofouling effects to the membrane which is always thought to be a serious limitation to the use of polyethersulfone in membrane technology. Chemical modification to the material is a promising solution to this problem. More specifically surface modification is an excellent technique to introduce hydrophilic properties and functional groups to the polyethersulfone membrane surface. This review covers chemical modifications of the polyethersulfone and covers different methods used to enhance the hydrophilicity of polyethersulfone membrane. In particular, the addition of amino functional groups to polyethersulfone is used as a fundamental method either to introduce hydrophilic properties or introduce nanomaterials to the surface of polyethersulfone membrane. This work reviews also previous research reports explored the use of amino functionalized polyethersulfone with different nanomaterials to induce biological activity and reduce fouling effects of the fabricated membrane.

2'-O-methylation in mRNA disrupts tRNA decoding during translation elongation.

PubMed

Choi, Junhong; Indrisiunaite, Gabriele; DeMirci, Hasan; Ieong, Ka-Weng; Wang, Jinfan; Petrov, Alexey; Prabhakar, Arjun; Rechavi, Gideon; Dominissini, Dan; He, Chuan; Ehrenberg, Måns; Puglisi, Joseph D

2018-03-01

Chemical modifications of mRNA may regulate many aspects of mRNA processing and protein synthesis. Recently, 2'-O-methylation of nucleotides was identified as a frequent modification in translated regions of human mRNA, showing enrichment in codons for certain amino acids. Here, using single-molecule, bulk kinetics and structural methods, we show that 2'-O-methylation within coding regions of mRNA disrupts key steps in codon reading during cognate tRNA selection. Our results suggest that 2'-O-methylation sterically perturbs interactions of ribosomal-monitoring bases (G530, A1492 and A1493) with cognate codon-anticodon helices, thereby inhibiting downstream GTP hydrolysis by elongation factor Tu (EF-Tu) and A-site tRNA accommodation, leading to excessive rejection of cognate aminoacylated tRNAs in initial selection and proofreading. Our current and prior findings highlight how chemical modifications of mRNA tune the dynamics of protein synthesis at different steps of translation elongation.

Magnetic resonance imaging for the exploitation of bubble-enhanced heating by high-intensity focused ultrasound: a feasibility study in ex vivo liver.

PubMed

Elbes, Delphine; Denost, Quentin; Robert, Benjamin; Köhler, Max O; Tanter, Mickaël; Bruno, Quesson

2014-05-01

Bubble-enhanced heating (BEH) may be exploited to improve the heating efficiency of high-intensity focused ultrasound in liver and to protect tissues located beyond the focal point. The objectives of this study, performed in ex vivo pig liver, were (i) to develop a method to determine the acoustic power threshold for induction of BEH from displacement images measured by magnetic resonance acoustic radiation force imaging (MR-ARFI), and (ii) to compare temperature distribution with MR thermometry for HIFU protocols with and without BEH. The acoustic threshold for generation of BEH was determined in ex vivo pig liver from MR-ARFI calibration curves of local tissue displacement resulting from sonication at different powers. Temperature distributions (MR thermometry) resulting from "conventional" sonications (20 W, 30 s) were compared with those from "composite" sonications performed at identical parameters, but after a HIFU burst pulse (0.5 s, acoustic power over the threshold for induction of BEH). Displacement images (MR-ARFI) were acquired between sonications to measure potential modifications of local tissue displacement associated with modifications of tissue acoustic characteristics induced by the burst HIFU pulse. The acoustic threshold for induction of BEH corresponded to a displacement amplitude of approximately 50 μm in ex vivo liver. The displacement and temperature images of the composite group exhibited a nearly spherical pattern, shifted approximately 4 mm toward the transducer, in contrast to elliptical shapes centered on the natural focal position for the conventional group. The gains in maximum temperature and displacement values were 1.5 and 2, and the full widths at half-maximum of the displacement data were 1.7 and 2.2 times larger than in the conventional group in directions perpendicular to ultrasound propagation axes. Combination of MR-ARFI and MR thermometry for calibration and exploitation of BEH appears to increase the efficiency and safety of HIFU treatment. Copyright © 2014 World Federation for Ultrasound in Medicine & Biology. Published by Elsevier Inc. All rights reserved.

Improved sensitivity by post-column chemical environment modification of CE-ESI-MS using a flow-through microvial interface.

PubMed

Risley, Jessica May; Chen, David Da Yong

2017-06-01

Post-column chemical environment modification can affect detection sensitivity and signal appearance when capillary electrophoresis is coupled through electrospray ionization to mass spectrometry (CE-ESI-MS). In this study, changes in the signal intensity and peak shape of N-Acetylneuraminic acid (Neu5Ac) were examined when the modifier solution used in a flow-through microvial interface for CE-ESI-MS was prepared using an acidic or basic background electrolyte (BGE) composition. The use of a basic modifier resulted in improved detection compared to the results obtained when an acidic modifier was used in negative ion mode. Increased sensitivity and more symmetrical peak shape were obtained. Using an acidic modifier, the LOD of Neu5Ac was 47.7 nM, whereas for a basic modifier, the LOD of Neu5Ac was 5.20 nM. The calculated asymmetry factor at 100 nM of Neu5Ac ranged from 0.71 to 1.5 when an acidic modifier was used, while the factor ranged from 1.0 to 1.1 when a basic modifier was used. Properly chosen post-column chemical modification can have a significant effect on the performance of the CE-MS system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal organic framework Cu9Cl2(cpa)6 as tunable molecular magnet

NASA Astrophysics Data System (ADS)

Hamilton, Heather S. C.; Farmer, William M.; Skinner, Samuel F.; ter Haar, Leonard W.

2018-05-01

Chemical modifications of the magnetic metal organic framework (MOF) Cu9X2(cpa)6.42H2O (X = F, Cl, Br; cpa = anion of 2-carboxypentonicacid) have been investigated as a means of modifying, in a tunable manner, the magnetism of this 2-D material best described as a triangles-in-triangles (TIT) or triangulated-Kagomé-latttice (TKL). Since numerous theoretical studies have already attempted to describe the enigmatic ground state of this Heisenberg lattice, tunable chemical modifications should provide an excellent opportunity to expand this class of materials for studies concerning fundamental physics of frustrated spins, and applications such as adiabatic demagnetization refrigeration (ADR) that depend on the magnetocaloric effect (MCE). The chemical modification investigated is the intercalation of d- and f-orbital ions into the voids of the framework (channels of nearly 20 Å diameter). Magnetic measurements in the temperature range 1.8 - 300 K confirm signature features of TKL magnetism in intercalated samples persist, specifically: i) large negative Weiss constant (θCW); ii) absence of a phase transition down to 1.8 K; iii) minimum in χMT; iv) low temperature χMT values increasingly divergent at low fields indicating net ferromagnetic correlations; and, v) increasing field dependence of magnetization at low temperatures suggestive of intermediate plateaus, or ferrimagnetism, not saturation.

Performance of basic kinematic thresholds in the identification of crash and near-crash events within naturalistic driving data.

PubMed

Perez, Miguel A; Sudweeks, Jeremy D; Sears, Edie; Antin, Jonathan; Lee, Suzanne; Hankey, Jonathan M; Dingus, Thomas A

2017-06-01

Understanding causal factors for traffic safety-critical events (e.g., crashes and near-crashes) is an important step in reducing their frequency and severity. Naturalistic driving data offers unparalleled insight into these factors, but requires identification of situations where crashes are present within large volumes of data. Sensitivity and specificity of these identification approaches are key to minimizing the resources required to validate candidate crash events. This investigation used data from the Second Strategic Highway Research Program Naturalistic Driving Study (SHRP 2 NDS) and the Canada Naturalistic Driving Study (CNDS) to develop and validate different kinematic thresholds that can be used to detect crash events. Results indicate that the sensitivity of many of these approaches can be quite low, but can be improved by selecting particular threshold levels based on detection performance. Additional improvements in these approaches are possible, and may involve leveraging combinations of different detection approaches, including advanced statistical techniques and artificial intelligence approaches, additional parameter modifications, and automation of validation processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reexamining X-mode suppression and fine structure in artificial E region field-aligned plasma density irregularities

NASA Astrophysics Data System (ADS)

Miceli, R. J.; Hysell, D. L.; Munk, J.; McCarrick, M.; Huba, J. D.

2013-09-01

Artificial field-aligned plasma density irregularities (FAIs) were generated in the E region of the ionosphere above the High Frequency Active Auroral Research Program facility during campaigns in May and August of 2012 and observed using a 30 MHz coherent scatter radar imager in Homer, Alaska. The purpose of this ionospheric modification experiment was to measure the threshold pump power required to excite thermal parametric instabilities by O-mode heating and to investigate the suppression of the FAIs by simultaneous X-mode heating. We find that the threshold pump power for irregularity excitation was consistent with theoretical predictions and increased by approximately a factor of 2 when X-mode heating was present. A modified version of the Another Model of the Ionosphere (SAMI2) ionospheric model was used to simulate the threshold experiments and suggested that the increase was entirely due to enhanced D region absorption associated with X-mode heating. Additionally, a remarkable degree of fine structure possibly caused by natural gradient drift instability in the heater-modified volume was observed in experiments performed during geomagnetically active conditions.

[Network of plastic neurons capable of forming conditioned reflexes ("membrane" model of learning)].

PubMed

Litvinov, E G; Frolov, A A

1978-01-01

Simple net neuronal model was suggested which was able to form the conditioning due to changes of the neuron excitability. The model was based on the following main concepts: (a) the conditioning formation should result in reduction of the firing threshold in the same neurons where the conditioning and reinforcement stimuli were converged, (b) neuron threshold may have only two possible states: initial and final ones, these were identical for all cells, the threshold may be changed only once from the initial value to the final one, (c) isomorphous relation may be introduced between some pair of arbitrary stimuli and some subset of the net neurons; any two pairs differing at least in one stimulus have unlike subsets of the convergent neurons. Stochastically organized neuronal net was used for analysis of the model. Considerable information capacity of the net gives the opportunity to consider that the conditioning formation is possible on the basis of the nervous cells. The efficienty of the model turn out to be comparable with the well known models where the conditioning formation was due to the modification of the synapses.

BSPS Program (ESI-Mass Spectrometry) Biological Sample Data Analysis; Disruption of Bacteria Spores

DTIC Science & Technology

2005-10-01

the original usage of the translational as a broad description of the entire process by which the polymer of the three-letter code in the mRNA is...translated. There is extensive review of post transnational modifications of proteins by Finn Wold(1981)24, given as in vivo chemical modifications... thiolation , biotin, bromination, carbamylation, deamidation, methylation, glu- cosylation, lipoyl, phosphorylation,, pyridoxal phosphate

Ferritin-Polymer Conjugates: Grafting Chemistry and Self-Assembly

DTIC Science & Technology

2009-10-26

a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. a...Chemoselective modification of M13 bacteriophage and cell imaging We systematically investigated the chemical modification of three kinds of reactive...tyrosine residues, on M13 surface. The reactivity for each group was identified by conjugation with small fluorescent molecules. Furthermore, the

Effects of different sterilization methods on the physico-chemical and bioresponsive properties of plasma-treated polycaprolactone films.

PubMed

Ghobeira, Rouba; Philips, Charlot; Declercq, Heidi; Cools, Pieter; De Geyter, Nathalie; Cornelissen, Ria; Morent, Rino

2017-01-24

For most tissue engineering applications, surface modification and sterilization of polymers are critical aspects determining the implant success. The first part of this study is thus dedicated to modifying polycaprolactone (PCL) surfaces via plasma treatment using a medium pressure dielectric barrier discharge, while the second part focuses on the sterilization of plasma-modified PCL. Chemical and physical surface changes are examined making use of water contact angle goniometry (WCA), x-ray photoelectron spectroscopy and atomic force microscopy. Bioresponsive properties are evaluated by performing cell culture tests. The results show that air and argon plasmas decrease the WCA significantly due to the incorporation of oxygen-containing functionalities onto the PCL surface, without modifying its morphology. Extended treatment times lead to PCL degradation, especially in the case of air plasma. In addition to surface modification, the plasma potential to sterilize PCL is studied with appropriate treatment times, but sterility has not been achieved so far. Therefore, plasma-modified films are subjected to UV, H 2 O 2 plasma (HP) and ethylene oxide (EtO) sterilizations. UV exposure of 3 h does not alter the PCL physico-chemical properties. A decreased wettability is observed after EtO sterilization, attributable to the modification of PCL chain ends reacting with EtO molecules. HP sterilization increases the WCA of the plasma-treated samples, presumably due to the scission of the hydrophilic bonds generated during the prior plasma treatments. Moreover, HP modifies the PCL surface morphology. For all the sterilizations, an improved cell adhesion and proliferation is observed on plasma-treated films compared to untreated ones. EtO shows the lowest proliferation rate compared to HP and UV. Overall, of the three sterilizations, UV is the most effective, since the physical alterations provoked by HP might interfere with the structural integrity when it comes to 3D scaffolds, and the chemical modifications caused by EtO, in addition to its toxicity, interfere with PCL bioactivity.

Modified NASA-Lewis chemical equilibrium code for MHD applications

NASA Technical Reports Server (NTRS)

Sacks, R. A.; Geyer, H. K.; Grammel, S. J.; Doss, E. D.

1979-01-01

A substantially modified version of the NASA-Lewis Chemical Equilibrium Code was recently developed. The modifications were designed to extend the power and convenience of the Code as a tool for performing combustor analysis for MHD systems studies. The effect of the programming details is described from a user point of view.

76 FR 50815 - TSCA Inventory Update Reporting Modifications; Chemical Data Reporting

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-16

... longer accept paper submissions or electronic media (i.e., as a file on a CD- ROM) for any CDR submission...-mail address: [email protected] . SUPPLEMENTARY INFORMATION: I. Does this action apply to me? You... byproduct chemical substance (NAICS codes 22, 322, 331, and 3344; e.g., utilities, paper manufacturing...

Fuels and chemicals from equine-waste-derived tail gas reactive pyrolysis oil: technoeconomic analysis, environmental and exergetic life cycle assessment

USDA-ARS?s Scientific Manuscript database

Horse manure, whose improper disposal imposes considerable environmental costs, constitutes an apt feedstock for conversion to renewable fuels and chemicals when tail gas reactive pyrolysis (TGRP) is employed. TGRP is a modification of fast pyrolysis that recycles its non-condensable gases and produ...

Physical and chemical basics of modification of poly(vinyl chloride) by means of polyisocyanate

NASA Astrophysics Data System (ADS)

Islamov, Anvar; Fakhrutdinova, Venera; Abdrakhmanova, Lyailya

2016-01-01

This research presents data relating to polyvinyl chloride (PVC) modification by means of reactive oligomer and measures technological, physical and mechanical properties of the modified composites. Polyisocyanate (PIC) has been chosen as the modifying reactive oligomer. It has been shown that insertion of the oligomer has a double effect on PVC. Primarily, PIC produces a plasticizing effect on PVC and in particular leads to an increase in thermal stability and melt flow index at the stage of processing. In addition, the molded PVC composites possess higher strength properties and lower deformability when exposed to temperature because of chemical transformations of PIC in polymer matrix and, as the result, the formation of cross-linked systems takes place. In this case, semi-interpenetrating structures are formed based on cross-linked products of PIC chemical transformations homogeneously distributed in the PVC matrix. It has been determined by means of IR-spectroscopy that the basic products of PIC curing are compounds with urea and biuret groups which leads to modifying effect on PVC especially: increase in strength, thermal and mechanical properties, and chemical resistance.

Synthetic Biological Approaches to Natural Product Biosynthesis

PubMed Central

Winter, Jaclyn M; Tang, Yi

2012-01-01

Small molecules produced in Nature continue to be an inspiration for the development of new therapeutic agents. These natural products possess exquisite chemical diversity, which gives rise to their wide range of biological activities. In their host organism, natural products are assembled and modified by dedicated biosynthetic pathways that Nature has meticulously developed. Often times, the complex structures or chemical modifications instated by these pathways are difficult to replicate using traditional synthetic methods. An alternative approach for creating or enhancing the structural variation of natural products is through combinatorial biosynthesis. By rationally reprogramming and manipulating the biosynthetic machinery responsible for their production, unnatural metabolites that were otherwise inaccessible can be obtained. Additionally, new chemical structures can be synthesized or derivatized by developing the enzymes that carry out these complicated chemical reactions into biocatalysts. In this review, we will discuss a variety of combinatorial biosynthetic strategies, their technical challenges, and highlight some recent (since 2007) examples of rationally designed unnatural metabolites, as well as platforms that have been established for the production and modification of clinically important pharmaceutical compounds. PMID:22221832

Improved chemical control for the Mexican rice borer (Lepidoptera: Crambidae) in sugarcane: Larval exposure, a novel scouting method, and efficacy of a single aerial insecticide application

USDA-ARS?s Scientific Manuscript database

A three-treatment aerial application insecticide experiment was conducted in five commercial sugarcane, Saccharum spp., fields in south Texas to evaluate the use of pheromone traps for improving chemical control of the Mexican rice borer, Eoreuma loftini (Dyar), in 2009 and 2010. A threshold of 20 m...

Inactivation of the cloned potassium channel mouse Kv1.1 by the human Kv3.4 'ball' peptide and its chemical modification.

PubMed Central

Stephens, G J; Robertson, B

1995-01-01

1. This study used the whole-cell patch clamp technique to investigate the action of a 28-mer 'inactivation peptide' based on part of the N-terminal sequence of the human Kv3.4 K+ channel (hKv3.4 peptide) on the cloned mouse brain K+ channel mKv1.1 expressed in Chinese hamster ovary (CHO) cells, and compared this with the inactivation produced by Shaker B inactivation peptide (ShB peptide). 2. Inclusion of the hKv3.4 peptide in the patch electrode (320 microM) transformed non-inactivating mKv1.1 into a rapidly inactivating current. The voltage dependence of time constants of decay and steady-state inactivation induced by hKv3.4 peptide were characteristic of an 'A-type' K+ current. 3. The hKv3.4 peptide had no effect on the voltage dependence of activation of mKv1.1, with a mid-point of activation of -8 mV, and a slope factor of 15 mV. Steady-state inactivation curves had a mid-point of inactivation of -36 mV and a slope factor of -7 mV; the time constant of recovery from inactivation at -90 mV was 1.3 s. 4. The chemical modification reagents N-bromoacetamide (NBA, 100 microM) and chloramine-T (CL-T, 500 microM) had no effect on the fast inactivation of mKv1.1 induced by ShB peptide. In contrast, the inactivation caused by hKv3.4 peptide was removed by brief exposure to NBA and CL-T. 5. Chemical modification resulted in a hyperpolarizing shift of -8 mV (CL-T) and -11 mV (NBA) in the voltage dependence of activation of mKv1.1 in the presence of hKv3.4 peptide. 6. Chemical modification was critically dependent on the presence of a cysteine residue at position 6, and not position 24, of hKv3.4 peptide. 7. NBA and CL-T caused only a slight inhibition of unmodified mKv1.1 current with no significant effect on the voltage dependence of mKv1.1 activation, and also had no effect on channel deactivation at -90 mV. 8. Chemical modification experiments were consistent with a selective action on the hKv3.4 peptide itself, specifically at the cysteine residue at position 6. PMID:7602512

Comparison of bioactive chemical space networks generated using substructure- and fingerprint-based measures of molecular similarity

NASA Astrophysics Data System (ADS)

Zhang, Bijun; Vogt, Martin; Maggiora, Gerald M.; Bajorath, Jürgen

2015-07-01

Chemical space networks (CSNs) have recently been introduced as a conceptual alternative to coordinate-based representations of chemical space. CSNs were initially designed as threshold networks using the Tanimoto coefficient as a continuous similarity measure. The analysis of CSNs generated from sets of bioactive compounds revealed that many statistical properties were strongly dependent on their edge density. While it was difficult to compare CSNs at pre-defined similarity threshold values, CSNs with constant edge density were directly comparable. In the current study, alternative CSN representations were constructed by applying the matched molecular pair (MMP) formalism as a substructure-based similarity criterion. For more than 150 compound activity classes, MMP-based CSNs (MMP-CSNs) were compared to corresponding threshold CSNs (THR-CSNs) at a constant edge density by applying different parameters from network science, measures of community structure distributions, and indicators of structure-activity relationship (SAR) information content. MMP-CSNs were found to be an attractive alternative to THR-CSNs, yielding low edge densities and well-resolved topologies. MMP-CSNs and corresponding THR-CSNs often had similar topology and closely corresponding community structures, although there was only limited overlap in similarity relationships. The homophily principle from network science was shown to affect MMP-CSNs and THR-CSNs in different ways, despite the presence of conserved topological features. Moreover, activity cliff distributions in alternative CSN designs markedly differed, which has important implications for SAR analysis.

Threshold kinetics of a solar-simulator-pumped iodine laser

NASA Technical Reports Server (NTRS)

Wilson, J. W.; Lee, Y.; Weaver, W. R.; Humes, D. H.; Lee, J. H.

1984-01-01

A model of the chemical kinetics of the n-C3F7I solar-simulator-pumped iodine laser is utilized to study the major kinetic processes associated with the threshold behavior of this experimental system. Excited-state diffusion to the cell wall is the dominant limiting factor below 5 torr. Excited-state diffusion to the cell wall is the dominant limiting factor below 5 torr. Excited-state recombination with the alkyl radical and quenching by the parent gas control threshold at higher pressures. Treatment of the hyperfine splitting and uncertainty in the pressure broadening are important factors in fixing the threshold level. In spite of scatter in the experimental data caused by instabilities in the simulator high-pressure high-pressure arc, reasonable agreement is achieved between the model and experiment. Model parameters arrived at are within the uncertainty range of values found in the literature.

Pressure Flammability Thresholds in Oxygen of Selected Aerospace Materials

NASA Technical Reports Server (NTRS)

Hirsch, David; Williams, Jim; Harper, Susana; Beeson, Harold; Ruff, Gary; Pedley, Mike

2010-01-01

The experimental approach consisted of concentrating the testing in the flammability transition zone following the Bruceton Up-and-Down Method. For attribute data, the method has been shown to be very repeatable and most efficient. Other methods for characterization of critical levels (Karberand Probit) were also considered. The data yielded the upward limiting pressure index (ULPI), the pressure level where approx.50% of materials self-extinguish in a given environment.Parametric flammability thresholds other than oxygen concentration can be determined with the methodology proposed for evaluating the MOC when extinguishment occurs. In this case, a pressure threshold in 99.8% oxygen was determined with the methodology and found to be 0.4 to 0.9 psia for typical spacecraft materials. Correlation of flammability thresholds obtained with chemical, hot wire, and other ignition sources will be conducted to provide recommendations for using alternate ignition sources to evaluate flammability of aerospace materials.

The Impact of Climate Change on Ozone-Related Mortality in Sydney

PubMed Central

Physick, William; Cope, Martin; Lee, Sunhee

2014-01-01

Coupled global, regional and chemical transport models are now being used with relative-risk functions to determine the impact of climate change on human health. Studies have been carried out for global and regional scales, and in our paper we examine the impact of climate change on ozone-related mortality at the local scale across an urban metropolis (Sydney, Australia). Using three coupled models, with a grid spacing of 3 km for the chemical transport model (CTM), and a mortality relative risk function of 1.0006 per 1 ppb increase in daily maximum 1-hour ozone concentration, we evaluated the change in ozone concentrations and mortality between decades 1996–2005 and 2051–2060. The global model was run with the A2 emissions scenario. As there is currently uncertainty regarding a threshold concentration below which ozone does not impact on mortality, we calculated mortality estimates for the three daily maximum 1-hr ozone concentration thresholds of 0, 25 and 40 ppb. The mortality increase for 2051–2060 ranges from 2.3% for a 0 ppb threshold to 27.3% for a 40 ppb threshold, although the numerical increases differ little. Our modeling approach is able to identify the variation in ozone-related mortality changes at a suburban scale, estimating that climate change could lead to an additional 55 to 65 deaths across Sydney in the decade 2051–2060. Interestingly, the largest increases do not correspond spatially to the largest ozone increases or the densest population centres. The distribution pattern of changes does not seem to vary with threshold value, while the magnitude only varies slightly. PMID:24419047

Pro-oxidant Induced DNA Damage in Human Lymphoblastoid Cells: Homeostatic Mechanisms of Genotoxic Tolerance

PubMed Central

Seager, Anna L.

2012-01-01

Oxidative stress contributes to many disease etiologies including ageing, neurodegeneration, and cancer, partly through DNA damage induction (genotoxicity). Understanding the i nteractions of free radicals with DNA is fundamental to discern mutation risks. In genetic toxicology, regulatory authorities consider that most genotoxins exhibit a linear relationship between dose and mutagenic response. Yet, homeostatic mechanisms, including DNA repair, that allow cells to tolerate low levels of genotoxic exposure exist. Acceptance of thresholds for genotoxicity has widespread consequences in terms of understanding cancer risk and regulating human exposure to chemicals/drugs. Three pro-oxidant chemicals, hydrogen peroxide (H2O2), potassium bromate (KBrO3), and menadione, were examined for low dose-response curves in human lymphoblastoid cells. DNA repair and antioxidant capacity were assessed as possible threshold mechanisms. H2O2 and KBrO3, but not menadione, exhibited thresholded responses, containing a range of nongenotoxic low doses. Levels of the DNA glycosylase 8-oxoguanine glycosylase were unchanged in response to pro- oxidant stress. DNA repair–focused gene expression arrays reported changes in ATM and BRCA1, involved in double-strand break repair, in response to low-dose pro-oxidant exposure; however, these alterations were not substantiated at the protein level. Determination of oxidatively induced DNA damage in H2O2-treated AHH-1 cells reported accumulation of thymine glycol above the genotoxic threshold. Further, the H2O2 dose-response curve was shifted by modulating the antioxidant glutathione. Hence, observed pro- oxidant thresholds were due to protective capacities of base excision repair enzymes and antioxidants against DNA damage, highlighting the importance of homeostatic mechanisms in “genotoxic tolerance.” PMID:22539617

Identification of ecological thresholds from variations in phytoplankton communities among lakes: contribution to the definition of environmental standards.

PubMed

Roubeix, Vincent; Danis, Pierre-Alain; Feret, Thibaut; Baudoin, Jean-Marc

2016-04-01

In aquatic ecosystems, the identification of ecological thresholds may be useful for managers as it can help to diagnose ecosystem health and to identify key levers to enable the success of preservation and restoration measures. A recent statistical method, gradient forest, based on random forests, was used to detect thresholds of phytoplankton community change in lakes along different environmental gradients. It performs exploratory analyses of multivariate biological and environmental data to estimate the location and importance of community thresholds along gradients. The method was applied to a data set of 224 French lakes which were characterized by 29 environmental variables and the mean abundances of 196 phytoplankton species. Results showed the high importance of geographic variables for the prediction of species abundances at the scale of the study. A second analysis was performed on a subset of lakes defined by geographic thresholds and presenting a higher biological homogeneity. Community thresholds were identified for the most important physico-chemical variables including water transparency, total phosphorus, ammonia, nitrates, and dissolved organic carbon. Gradient forest appeared as a powerful method at a first exploratory step, to detect ecological thresholds at large spatial scale. The thresholds that were identified here must be reinforced by the separate analysis of other aquatic communities and may be used then to set protective environmental standards after consideration of natural variability among lakes.

Synthesis of (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine enabled by photoredox catalysis in flow.

PubMed

Beatty, Joel W; Stephenson, Corey R J

2014-07-23

Natural product modification with photoredox catalysis allows for mild, chemoselective access to a wide array of related structures in complex areas of chemical space, providing the possibility for novel structural motifs as well as useful quantities of less abundant congeners. While amine additives have been used extensively as stoichiometric electron donors for photocatalysis, the controlled modification of amine substrates through single-electron oxidation is ideal for the synthesis and modification of alkaloids. Here, we report the conversion of the amine (+)-catharanthine into the natural products (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine utilizing visible light photoredox catalysis.

Surface modification of titanium and titanium alloys by ion implantation.

PubMed

Rautray, Tapash R; Narayanan, R; Kwon, Tae-Yub; Kim, Kyo-Han

2010-05-01

Titanium and titanium alloys are widely used in biomedical devices and components, especially as hard tissue replacements as well as in cardiac and cardiovascular applications, because of their desirable properties, such as relatively low modulus, good fatigue strength, formability, machinability, corrosion resistance, and biocompatibility. However, titanium and its alloys cannot meet all of the clinical requirements. Therefore, to improve the biological, chemical, and mechanical properties, surface modification is often performed. In view of this, the current review casts new light on surface modification of titanium and titanium alloys by ion beam implantation. (c) 2010 Wiley Periodicals, Inc.

Chemical stimulation of adherent cells by localized application of acetylcholine from a microfluidic system.

PubMed

Zibek, Susanne; Hagmeyer, Britta; Stett, Alfred; Stelzle, Martin

2010-01-01

Chemical stimulation of cells is inherently cell type selective in contrast to electro-stimulation. The availability of a system for localized application of minute amounts of chemical stimulants could be useful for dose related response studies to test new compounds. It could also bring forward the development of a novel type of neuroprostheses. In an experimental setup microdroplets of an acetylcholine solution were ejected from a fluidic microsystem and applied to the bottom of a nanoporous membrane. The solution traveled through the pores to the top of the membrane on which TE671 cells were cultivated. Calcium imaging was used to visualize cellular response with temporal and spatial resolution. Experimental demonstration of chemical stimulation for both threshold gated stimulation as well as accumulated dose-response was achieved by either employing acetylcholine as chemical stimulant or applying calcein uptake, respectively. Numerical modeling and simulation of transport mechanisms involved were employed to gain a theoretical understanding of the influence of pore size, concentration of stimulant and droplet volume on the spatial-temporal distribution of stimulant and on the cellular response. Diffusion, pressure driven flow and evaporation effects were taken into account. Fast stimulation kinetic is achieved with pores of 0.82 μm diameter, whereas sustained substance delivery is obtained with nanoporous membranes. In all cases threshold concentrations ranging from 0.01 to 0.015 μM acetylcholine independent of pore size were determined.

Selective generation of laser-induced periodic surface structures on Al2O3-ZrO2-Nb composites

NASA Astrophysics Data System (ADS)

Kunz, Clemens; Bartolomé, José F.; Gnecco, Enrico; Müller, Frank A.; Gräf, Stephan

2018-03-01

Laser-induced periodic surface structures (LIPSS) were selectively fabricated on the metal phase of Al2O3-nZrO2-Nb (78.3-1.7-20 vol.%) ceramic matrix composites. For this purpose, sample surfaces were irradiated with fs-laser pulses (τ = 300 fs, λ = 1025 nm) of different laser peak fluences ranging from 0.23 to 0.40 J/cm2. The structured surfaces were characterised by scanning electron microscopy (SEM), atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and by measuring the water contact angle. Well-pronounced LIPSS with a period of Λ ≈ 750 nm and a height of h ≈ 263 nm were found solely on the metal phase of the composite when applying the highest fluence whereas no structural and chemical modifications were found on the surface of the ceramic matrix. This can be explained by the different light absorption behaviour of both phases, which results in different ablation thresholds. The water contact angle of composite surfaces was successfully reduced from 68.4° for untreated samples to 40.9° for structured samples. Selectively structured composites with adjustable wettability are of particular interest for biomedical and tribological applications.

Deproteinised natural rubber latex grafted poly(dimethylaminoethyl methacrylate) - poly(vinyl alcohol) blend membranes: Synthesis, properties and application.

PubMed

Jayadevan, Janisha; Alex, Rosamma; Gopalakrishnapanicker, Unnikrishnan

2018-02-01

Natural rubber latex was initially deproteinised (DNRL) and then subjected to physicochemical modifications to make high functional membranes for drug delivery applications. Initially, DNRL was prepared by incubating with urea, sodiumdodecylsulphate and acetone followed by centrifugation. The deproteinisation was confirmed by CHN analysis. The DNRL was then chemically modified by grafting (dimethylaminoethyl methacrylate) onto NR particles by using a redox initiator system viz; cumene hydroperoxide/tetraethylenepentamine, followed by dialysis for purification. The grafting was confirmed by dynamic light scattering, Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The grafted system was blended with a hydrophilic adhesive polymer PVA and casted into membranes. The membranes after blending showed enhanced mechanical properties with a threshold concentration of PVA. The moisture uptake, swelling and water contact angle experiments indicated an increased hydrophilicity with an increased PVA content in the blend membranes. The grafted DNRL possessed significant antibacterial property which has been found to be retained in the blended form. A notable decrease in cytotoxicity was observed for the modified DNRL membranes than the bare DNRL membranes. The in-vitro drug release studies using rhodamine B as a model drug, confirmed the utility of the prepared membranes to function as a drug delivery matrix. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly stable precursor solution containing ZnO nanoparticles for the preparation of ZnO thin film transistors.

PubMed

Huang, Heh-Chang; Hsieh, Tsung-Eong

2010-07-23

ZnO particles with an average size of about 5 nm were prepared via a sol-gel chemical route and the silane coupling agent, (3-glycidyloxypropyl)-trimethoxysilane (GPTS), was adopted to enhance the dispersion of the ZnO nanoparticles in ethyl glycol (EG) solution. A ZnO surface potential as high as 66 mV was observed and a sedimentation test showed that the ZnO precursor solution remains transparent for six months of storage, elucidating the success of surface modification on ZnO nanoparticles. The ZnO thin films were then prepared by spin coating the precursor solution on a Si wafer and annealing treatments at temperatures up to 500 degrees C were performed for subsequent preparation of ZnO thin film transistors (TFTs). Microstructure characterization revealed that the coalescence of ZnO nanoparticles occurs at temperatures as low as 200 degrees C to result in a highly uniform, nearly pore-free layer. However, annealing at higher temperatures was required to remove organic residues in the ZnO layer for satisfactory device performance. The 500 degrees C-annealed ZnO TFT sample exhibited the best electrical properties with on/off ratio = 10(5), threshold voltage = 17.1 V and mobility (micro) = 0.104 cm(2) V(-1) s(-1).

Effects of Thickness, Pulse Duration, and Size of Strip Electrode on Ferroelectric Electron Emission of Lead Zirconate Titanate Films

NASA Astrophysics Data System (ADS)

Yaseen, Muhammad; Ren, Wei; Chen, Xiaofeng; Feng, Yujun; Shi, Peng; Wu, Xiaoqing

2018-02-01

Sol-gel-derived lead zirconate titanate (PZT) thin-film emitters with thickness up to 9.8 μm have been prepared on Pt/TiO2/SiO2/Si wafer via chemical solution deposition with/without polyvinylpyrrolidone (PVP) modification, and the relationship between the film thickness and electron emission investigated. Notable electron emission was observed on application of a trigger voltage of 120 V for PZT film with thickness of 1.1 μm. Increasing the film thickness decreased the threshold field to initiate electron emission for non-PVP-modified films. In contrast, the electron emission behavior of PVP-modified films did not show significant dependence on film thickness, probably due to their porous structure. The emission current increased with decreasing strip width and space between strips. Furthermore, it was observed that increasing the duration of the applied pulse increased the magnitude of the emission current. The stray field on the PZT film thickness was also calculated and found to increase with increasing ferroelectric sample thickness. The PZT emitters were found to be fatigue free up to 105 emission cycles. Saturated emission current of around 25 mA to 30 mA was achieved for the electrode pattern used in this work.

Maps showing predicted probabilities for selected dissolved oxygen and dissolved manganese threshold events in depth zones used by the domestic and public drinking water supply wells, Central Valley, California

USGS Publications Warehouse

Rosecrans, Celia Z.; Nolan, Bernard T.; Gronberg, JoAnn M.

2018-01-31

The purpose of the prediction grids for selected redox constituents—dissolved oxygen and dissolved manganese—are intended to provide an understanding of groundwater-quality conditions at the domestic and public-supply drinking water depths. The chemical quality of groundwater and the fate of many contaminants is influenced by redox processes in all aquifers, and understanding the redox conditions horizontally and vertically is critical in evaluating groundwater quality. The redox condition of groundwater—whether oxic (oxygen present) or anoxic (oxygen absent)—strongly influences the oxidation state of a chemical in groundwater. The anoxic dissolved oxygen thresholds of <0.5 milligram per liter (mg/L), <1.0 mg/L, and <2.0 mg/L were selected to apply broadly to regional groundwater-quality investigations. Although the presence of dissolved manganese in groundwater indicates strongly reducing (anoxic) groundwater conditions, it is also considered a “nuisance” constituent in drinking water, making drinking water undesirable with respect to taste, staining, or scaling. Three dissolved manganese thresholds, <50 micrograms per liter (µg/L), <150 µg/L, and <300 µg/L, were selected to create predicted probabilities of exceedances in depth zones used by domestic and public-supply water wells. The 50 µg/L event threshold represents the secondary maximum contaminant level (SMCL) benchmark for manganese (U.S. Environmental Protection Agency, 2017; California Division of Drinking Water, 2014), whereas the 300 µg/L event threshold represents the U.S. Geological Survey (USGS) health-based screening level (HBSL) benchmark, used to put measured concentrations of drinking-water contaminants into a human-health context (Toccalino and others, 2014). The 150 µg/L event threshold represents one-half the USGS HBSL. The resultant dissolved oxygen and dissolved manganese prediction grids may be of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to anoxic conditions. Prediction grids for selected redox constituents and thresholds were created by the USGS National Water-Quality Assessment (NAWQA) modeling and mapping team.

Mid-infrared spectroscopy and chemometrics in corn starch classification

NASA Astrophysics Data System (ADS)

Dupuy, N.; Wojciechowski, C.; Ta, C. D.; Huvenne, J. P.; Legrand, P.

1997-06-01

The authentication of food is a very important issue for both the consumer and the food industry at all levels of the food chain from raw materials to finished products. Corn starch can be used in a wide variety of food preparations such as bakery cream fillings, sauces, salad dressings, frozen foods etc. Many modifications are made to corn starch in connection with its use in agrofood. The value of the product increases with the degree of modification. Some chemical and physical tests have been devised to solve the problem of identifying these modifications but all the methods are time consuming and require skilled operators. We separate corn starches into groups related to their modification on the basis of the infrared spectra.

Nonlinear distortion analysis for single heterojunction GaAs HEMT with frequency and temperature

NASA Astrophysics Data System (ADS)

Alim, Mohammad A.; Ali, Mayahsa M.; Rezazadeh, Ali A.

2018-07-01

Nonlinearity analysis using two-tone intermodulation distortion (IMD) technique for 0.5 μm gate-length AlGaAs/GaAs based high electron mobility transistor have been investigated based on biasing conditions, input power, frequency and temperature. The outcomes indicate a significant modification on the output IMD power and as well as the minimum distortion level. The input IMD power effects the output current and subsequently the threshold voltage reduces, resulting to an increment in the output IMD power. Both frequency and temperature reduces the magnitude of the output IMDs. In addition, the threshold voltage response with temperature alters the notch point of the nonlinear output IMD’s accordingly. The aforementioned investigation will help the circuit designers to evaluate the best biasing option in terms of minimum distortion, maximum gain for future design optimizations.